CN105102224B - Film and tape label plastic containers - Google Patents

Film and tape label plastic containers Download PDF

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Publication number
CN105102224B
CN105102224B CN201480000827.0A CN201480000827A CN105102224B CN 105102224 B CN105102224 B CN 105102224B CN 201480000827 A CN201480000827 A CN 201480000827A CN 105102224 B CN105102224 B CN 105102224B
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CN
China
Prior art keywords
film
porous layer
layer
thermoplastic resin
plastic containers
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CN201480000827.0A
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Chinese (zh)
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CN105102224A (en
Inventor
铃木达也
中村纲
上田隆彦
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Yupo Corp
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Yupo Corp
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C2045/1486—Details, accessories and auxiliary operations
    • B29C2045/14901—Coating a sheet-like insert smaller than the dimensions of the adjacent mould wall
    • B29C2045/14918—Coating a sheet-like insert smaller than the dimensions of the adjacent mould wall in-mould-labelling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14778—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles the article consisting of a material with particular properties, e.g. porous, brittle
    • B29C45/14811—Multilayered articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/104—Oxysalt, e.g. carbonate, sulfate, phosphate or nitrate particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/304—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/516—Oriented mono-axially
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/72—Density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/75—Printability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2519/00—Labels, badges
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1376—Foam or porous material containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495—Thickness [relative or absolute]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249982—With component specified as adhesive or bonding agent
    • Y10T428/249983—As outermost component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249986—Void-containing component contains also a solid fiber or solid particle

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Inorganic Chemistry (AREA)
  • Details Of Rigid Or Semi-Rigid Containers (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The present invention provides a kind of excellent thermoplastic resin membrane of thermal insulation and the tape label plastic containers for attaching the thermoplastic resin membrane by in-molded, and the thermoplastic resin membrane has the porous layer of at least 1 layer condition for meeting following (A) and (B).(A) porous layer includes the mass parts of thermoplastic resin 25~65 and the mass parts of inorganic fine powder 35~75.(B) L=d × (ρ is used0‑ρ)/ρ0The emptying aperture length L of the porous layer of expression is more than 20 μm.In addition, L is emptying aperture length [μm], d is the thickness [μm] of porous layer, and ρ is the density [g/cm of porous layer3], ρ0For the real density [g/cm of porous layer3]。

Description

Film and tape label plastic containers
Technical field
The present invention relates to thermoplastic resin membrane.More particularly to the excellent thermoplastic resin membrane of thermal insulation, by mould It is molded and attaches the tape label plastic containers of the thermoplastic resin membrane.
Background technology
It is known that label is set by in-molded on plastic containers.It is known for example, including ethylene copolymer bonding layer In-mold shaping label (patent document 1), on heat sealability resin bed implement Embossing processing in-mold shaping label (patent document 2), comprising ethyleneα-olefincopolymer as heat sealability resin bed main component in-mold shaping label (patent document 3), with Polyethyleneimine is thermoplastic resin membrane's (patent document 4) of main component.
Prior art literature
Patent document
Patent document 1：No. 4,837,075 specifications of U.S. Patent No.
Patent document 2：Japanese Patent Publication 1-105960 publications
Patent document 3：Japanese Unexamined Patent Publication 9-207166 publications
Patent document 4：Japanese Unexamined Patent Publication 2000-290411 publications
The content of the invention
Problems to be solved by the invention
According to the combination of the species of in-molded method and the material of in-mold shaping label, engagement is produced sometimes bad.
The solution used to solve the problem
A kind of film is provided in the first form of the present invention, it is characterised in that it is the film containing thermoplastic resin, tool There is the porous layer of at least 1 layer condition for meeting following (A) and (B)：
(A) previous porous matter layer includes the mass parts of thermoplastic resin 25~65 and the mass parts of inorganic fine powder 35~75；
(B) the emptying aperture length L of porous layer shown in following formula (1) is more than 20 μm.
L=d × (ρ0-ρ)/ρ0Formula (1)
In formula (1), L is emptying aperture length [μm], and d is the thickness [μm] of porous layer, and ρ is the density [g/ of porous layer cm3], ρ0For the real density [g/cm of porous layer3]。
Above-mentioned film can further meet the condition of following (C)：
(C) thickness d of previous porous matter layer is the 10~100% of the thickness D of aforementioned film.
In above-mentioned film, porous layer can relative to thermoplastic resin and inorganic fine powder total 100 mass Part includes the mass parts of additive 0.1~5.In above-mentioned film, in the section parallel with the thickness direction of porous layer from The ultimate range that the surface of inorganic fine powder starts untill emptying aperture wall can be less than 50 μm.
In above-mentioned film, the void content p shown in the formula (2) of porous layer can be 15~75%；
P=(ρ0-ρ)/ρ0× 100 formulas (2)
In formula (2), p is the void content [%] of Porous, and ρ is the density [g/cm of porous layer3], ρ0For porous layer Real density [g/cm3]。
In above-mentioned film, contained thermoplastic resin can be using polyolefin as main component in porous layer.Above-mentioned thin In film, porous layer can be along the layer that at least a direction of principal axis is stretched.In above-mentioned film, the thickness D of film can be with For 40~250 μm.In above-mentioned film, the surface resistivity R at least one face of filmsCan be under the conditions of 23 DEG C of 50%RH For 1 × 108~1 × 1012Ω.Above-mentioned film can also have the superficial layer set on a surface side of porous layer.Upper State in film, the surface printing information of the layer set on a surface side of the porous layer of film.
Above-mentioned film also has the bonding layer set on a surface side of porous layer.In above-mentioned film, bonding layer Surface according to JIS P 8119:The 1998 Wang Yan formula smoothnesses s determined can be 5~4000 seconds.Above-mentioned film can be with With the superficial layer set on another surface side of porous layer.In above-mentioned film, the porous layer of film another The surface of the layer set on surface side can print information.In above-mentioned film, the table of another surface side of the porous layer of film The surface resistivity R in facesCan be 1 × 10 under conditions of 23 DEG C of 50%RH12More than Ω.
In above-mentioned film, the thermal resistance value R shown in the following formula (3) of filmtCan be 0.05m2More than K/W：
Rt=D × 10-6/ λ formulas (3)
In formula (3), RtFor the thermal resistance value [m of film2K/W], D is the thickness [μm] of film, and λ is the thermal conductivity [W/ of film m·K]。
A kind of tape label plastic containers are provided in the second form of the present invention, it is pasted with above-mentioned by in-molded Film.
Above-mentioned tape label plastic containers can meet the relation of following formula (4)：
Tf-10≤Tv≤Tf+60 formulas (4)
In formula (4), the fusing point of Tv thermoplastic resins contained by the outmost surface of the container body of tape label plastic containers, Tf For the fusing point of the thermoplastic resin contained by the layer being in contact with container body of film.
A kind of film is provided in the 3rd form of the present invention, it is characterised in that it is the film containing thermoplastic resin, With at least one layer of porous layer, porous layer includes the mass parts of thermoplastic resin 25~65 and inorganic fine powder 35~75 Mass parts, the void content p shown in the following formula (2) of Porous is 15~75%.
P=(ρ0-ρ)/ρ0× 100 formulas (2)
In formula (2), p is the void content [%] of previous porous matter, and ρ is the density [g/cm of previous porous matter layer3], ρ0To be preceding State the real density [g/cm of porous layer3]。
A kind of film is provided in the 4th form of the present invention, it is characterised in that it is the film containing thermoplastic resin, tool There are at least one layer of porous layer, the thermal resistance value R shown in the following formula (3) of the filmtFor 0.05m2More than K/W.
Rt=D × 10-6/ λ formulas (3)
In previously described formula (3), RtFor the thermal resistance value [m of aforementioned film2K/W], D is the thickness [μm] of aforementioned film, before λ is State the thermal conductivity [W/mK] of film.
A kind of in-mold shaping label is provided in the 5th form of the present invention, it has at least one layer of porous layer, and this is more Hole matter layer includes the mass parts of thermoplastic resin 25~65 and the mass parts of inorganic fine powder 35~75.
The effect of invention
The label good with the zygosity of container body can be provided.It can provide by in-molded in container body Orange peel effect (orange peel) label is not likely to produce during upper attachment labels.
Embodiment
The present invention described further below, the explanation of described structure important document is one of embodiments of the present invention below (typical example), is not particularly limited to their content.A variety of changes or modifications can be subject in the above-described embodiment, this It is that those skilled in the art are clear.In addition, technically in reconcilable scope, for the thing illustrated by particular implementation Item can also be applied to other embodiment.The form for being subject to this changes or modifications can also reside in the technical scope of the present invention Interior, this can be clear and definite according to the record of claim.In addition, in the present invention, when being marked as "~", referring to comprising before and after it Described numerical value is respectively as minimum value and the scope of maximum.In addition, when labeled as 23 DEG C of 30%RH, referring to temperature 23 DEG C, the environment of relative humidity 30%.
<Tape label plastic containers>
In the present embodiment, tape label plastic containers have container body and label.Label is for example by container master Adhered film on body and formed.
(preparation methods of tape label plastic containers)
The tape label plastic containers of present embodiment are for example made up of in-molded method.More specifically, in die inside Face on be configured with after film (otherwise referred to as in-mold shaping label), by the heat that plastic state is injected into the mould Thermoplastic resin composition and be made.Blow molding method, injection molding method etc. can be included as in-molded method.
For example, according to blow molding method, film to be configured to the appropriate location in mould first.Then it is made by above-mentioned heat Precast body or parison that thermoplastic resin composition is constituted.Then, to prefabricated in the state of precast body or parison is clamped with mould Compressed gas is blown into inside body or parison, precast body or parison is expanded in mould.Hereafter, by being cooled and shaped product so as to obtain To tape label plastic containers.
(properties of tape label plastic containers)
In in-molded method, for forming the resin of container body from molten condition (sometimes referred to as molten resin) and using It is in contact in the film for forming label.Now, be present in the container body side of film surface resin melt, with container master Be cooled solidification after body integration, so that film is attached on container body.Therefore, if the thermal insulation of film is not enough, The heat for being then transmitted to film from molten resin can be conducted to mould, so as to can not make the table of container body side for being present in film The resin in face fully melts.As a result, film is not exclusively engaged with container body, even if or film connect with container body Conjunction can not obtain the bond strength of resistance to practicality.
The method bad as above-mentioned engagement is suppressed, considers using with by with thermoplastic resin as in-mold shaping label The substrate layer and the layered product of bonding layer constituted for the porous film of main component.In addition, " main component " refers in institute In total content (100 mass %) containing composition, content is more than 50 mass % composition.Now, due to the thermal resistivity of substrate layer It is larger, after in-mold shaping label is configured in mould bonding layer is in contact with molten resin, when being injected in mould During molten resin, the heat that can suppress to conduct to bonding layer from molten resin is conducted to mould.So as to will be in-molded Label is attached securely with container body.
However, as the substrate layer of in-mold shaping label, when using, the Porous using thermoplastic resin as main component is thin During film, the air enclosed in shaping in porous film carries out thermal expansion.As a result, the emptying aperture included in porous film Wall can torsional deformation, the easy generation bumps (sometimes referred to as orange peel effect) on the surface of in-mold shaping label.In addition, if going out The density of porous film is reduced in the purpose for the thermal insulation for improving in-mold shaping label, because emptying aperture footpath becomes big, emptying aperture wall Easily distortion, therefore encouraged the generation of orange peel effect.Therefore, when using base material of the porous film as in-mold shaping label During layer, it is difficult to take into account zygosity and the suppression of orange peel effect of in-mold shaping label and container body.
On the other hand, it is known that the synthetic paper containing the thermoplastic resin composition containing a large amount of inorganic substances powder.For example exist A kind of diaphragm is disclosed in Japanese Unexamined Patent Publication 2013-010931 publications, makes containing 60 mass %~82 mass % inorganic matter The raw material of the mass % of the mass % of matter powder, 18 mass %~40 thermoplastic resin, 0.05 mass %~4.0 adjuvant passes through Die head carries out extrusion forming so as to forming diaphragm intermediate by T modulus methods, by by diaphragm intermediate with specific stretching ratio Stretched and carry out apparent specific gravity adjustment.
Usually, the thermal conductivity of inorganic fine powder is more than the thermal conductivity of thermoplastic resin.It is taken as that it is difficult to will include The thermoplastic resin composition of a large amount of inorganic substances is applied to require the purposes of thermal insulation.With it in this way, will be containing a large amount of inorganic The thermoplastic resin composition of attritive powder is used for the purposes for playing its thermal conductivity.For example, for raising mobile phone housing The purpose of thermal diffusivity and use the thermoplastic resin composition containing a large amount of inorganic fine powders.In fact, in Japanese Unexamined Patent Publication Although refer to the printing adaptability of synthetic paper, flexibility (adaptability) of operation and water resistance in 2013-010931 publications, also do not teach Lead the record about thermal insulation.Moreover, although the purposes on synthetic paper describes many purposes, but as in-mold shaping label that Sample requires that the purposes of thermal insulation is not recorded.
The present inventor etc. has found by diligent research institute, by possessing the Porous containing relatively large inorganic fine powder Void content (otherwise referred to as voidage), emptying aperture length and the thermal conductivity of adjustment porous layer and film in the film of layer At least one in thermal conductivity and thermal resistance value, so as to which the film is used as into in-mold shaping label.In addition, the present inventors is also It was found that, it can take into account zygosity and the tangerine of in-mold shaping label and container body by the way that the film is used as into in-mold shaping label The suppression of skin phenomenon.
According to present embodiment, by thermal insulation is excellent, thermoplastic resin membranes containing a large amount of inorganic substances powder are used as In-mold shaping label.So as to take into account the zygosity of in-mold shaping label and container body and the suppression of orange peel effect.From And obtain the excellent tape label plastic containers of the bond strength between in-mold shaping label and container body.And obtain almost not Produce the excellent tape label plastic containers of orange peel effect, aesthetic property.
In addition, according to blow molding method, film can be attached at appearance while the container body of molded plastic container In device main body.Therefore, it is possible to maintain aesthetic appearance, lightweight and the productivity ratio of container body constant, easily manufacture in a short time Tape label plastic containers.However, when tape label plastic containers are made using blow molding method, with being made of injection molding method The situation of tape label plastic containers is compared, and it is less to conduct heat conduction amount to film from thermoplastic resin composition.Therefore, with passing through The situation that tape label plastic containers are made in injection molding method is compared, and easily produces engagement bad.
However, by present embodiment, by thermal insulation is excellent, thermoplastic resin membranes containing a large amount of inorganic substances powder As in-mold shaping label.So as to improve the zygosity of in-mold shaping label.As a result, even in using blow molding legal system In the case of making tape label plastic containers, it can also suppress engagement bad.
Illustrated for each several part of the tape label plastic containers of present embodiment.First, to the thin of container body After section is illustrated, the details for in-mold shaping label is illustrated.
<Container body>
The material of container body is not limited, and can use well known materials.The forming method of container body is not limited, can To use the known method of forming.
(container material)
The material of container body can be that can be molded the material of hollow container.As the material of container body, for example, make Use thermoplastic resin.It can be enumerated as thermoplastic resin：Polyethylene terephthalate (PET) or its copolymer, poly- carbon The polyester resins such as acid ester resin；Polyolefin resins such as polypropylene (PP), polyethylene (PE) etc..When using blow molding legal system During into tape label plastic containers, polyolefin resin is preferably used.As the material of container body, it can also use with above-mentioned heat Plastic resin is the thermoplastic resin composition of main component.
The material of container body is selected to meet following formula.So as to further improve in-mold shaping label and modeling Engaging force between material container.
Tf-10≦Tv≦Tf+60
Herein, the fusing point of Tv thermoplastic resins contained by the container body surface of plastic containers.Tf for film and container Main body is in contact the fusing point of thermoplastic resin contained by the surface of side.Especially when Tf is thermoplastic resin contained by aftermentioned porous layer Fusing point when, even if in-mold shaping label the container body side of porous layer face do not have bonding layer in the case of, also can Suppress coarse and orange peel effect.
<The structure of film>
In the present embodiment, film has at least 1 layer porous layer.Film can also be further porous with being arranged at Superficial layer on one surface side of matter layer.Film can also further have the surface being arranged on a surface side of porous layer to apply Coating.Film can also further have the bonding layer for a surface side for being arranged at porous layer.When film has bonding layer, At least one of superficial layer and surface coating layer can be configured at being not provided with the surface side of bonding layer of porous layer.Engagement Layer can be in contact configuration with the one side of above-mentioned porous layer.Superficial layer or surface coating layer can be another with above-mentioned porous layer One face is in contact configuration.
[porous layer]
In the present embodiment, porous layer includes thermoplastic resin and inorganic fine powder.Porous layer can also be wrapped Containing additive.
(thermoplastic resin)
As long as thermoplastic resin contained by porous layer can be shaped to the material of film-form, its species is not done especially Limitation.It can be enumerated as thermoplastic resin contained by porous layer：High density polyethylene (HDPE), medium density polyethylene, low density polyethylene The olefine kind resins such as alkene, polypropylene, propylene class copolymer resins, poly- Methyl-1-pentene, ethene cyclic olefin copolymer；Second Alkene vinyl acetate co-polymer, ethylene acrylic acid co polymer, maleic acid modified polyethylene, maleated polypropylene etc. contain The vistanex of functional group；The phenylethylene tree such as random polystyrene, syndiotactic polytyrene, styrene-maleic acid copolymer Fat；Polyethylene terephthalate, polyethylene terephthalate/ethylene isophthalate, poly terephthalic acid The esters resins such as fourth diester, poly butylene succinate, poly adipate succinic acid ester, PLA, makrolon；Nylon-6, Buddhist nun Imperial -6,6 grade acid amides resinoids；Mixture more than two species of these resins etc..
Thermoplastic resin contained by porous layer preferably comprises olefine kind resin as main component.It is excellent so as to obtain processability Good porous layer.Above-mentioned olefine kind resin can also be：The homopolymer of alkene, the copolymer of two or more alkene or alkene With copolymer that can be with the monomer of olefin-copolymerization.As can be enumerated with the monomer of olefin-copolymerization：1- butylene, 1- hexenes, 1- The alpha-olefins such as heptene, 1- octenes, 4-methyl-1-pentene；Vinylacetate, acrylic acid, maleic anhydride etc..Copolymer can be nothing Advise copolymer, or block copolymer.Above-mentioned olefine kind resin can be polythylene resin or propylene resin.So as to Obtain the porous layer of chemical reagent resistance, processability and economical.
Above-mentioned olefine kind resin can be the olefine kind resin through graft modification.The method of graft modification, which is for example enumerated, makes alkene Hydrocarbon resins or olefine kind resin containing functional group and unsaturated carboxylic acid or derivatives thereof are sent out in the presence of an oxidant The method of raw reaction.It can be enumerated as oxidant：The peroxy acids such as Peracetic acid, persulfuric acid, potassium peroxydisulfate and its metal salt；It is smelly Oxygen etc..Olefine kind resin of the graft modification rate relative to olefine kind resin or containing functional group can be 0.005~10 mass %, Preferably 0.01~5 mass %.
As thermoplastic resin contained by porous layer, by being used in mixed way, two or more thermoplastic resins, is improved By it is thermoplastic resin molded be film-form when mobility, mouldability etc..In one embodiment, in the formation of porous layer In process, when being compounded a large amount of inorganic fine powders into thermoplastic resin, thermoplastic resin and inorganic microfine powder are made sometimes The mobility of the mixing fused mass at end declines, so as to be difficult to form porous layer.By combining the thermoplastic resin of different viscosities, Even if being compounded a large amount of inorganic fine powders into thermoplastic resin, it can also suppress the mixing of thermoplastic resin and inorganic fine powder The reduction of the mobility of fused mass.In another embodiment, by being compounded into the thermoplastic resin as main component The thermoplastic resin of super high molecular weight, or compounding fusing point are used for thermoplastic resin (for example, HDPE of main component.) low by 10 Resin (being, for example, LDPE) more than DEG C, it is in uneven thickness when can suppress to stretch.
The content of thermoplastic resin in porous layer can be integrally more than 25 mass % relative to porous layer.So as to Improve the drawing stability of the porous layer when porous layer is being shaped into film-form.Thermoplastic resin in porous layer The content of fat can be integrally more than 28 mass %, preferably more than 30 mass % relative to porous layer.
The content of thermoplastic resin in porous layer can be integrally below 65 mass % relative to porous layer.Now Obtain opacity or the big porous layer of whiteness.The content of thermoplastic resin in porous layer is whole relative to porous layer Body can be below 63 mass %, preferably below 60 mass %.
(inorganic fine powder)
Enumerated as inorganic fine powder contained by porous layer from calcium carbonate, calcined clay, silica, diatomite, carclazyte, cunning Stone, titanium dioxide, barium sulfate, aluminum oxide, zeolite, mica, sericite, bentonite, sepiolite, vermiculite, dolomite, wollastonite, Selected in the group of the compositions such as aluminium hydroxide, glass fibre more than one.When porous layer contains calcium carbonate, talcum and titanium oxide In it is at least one kind of when, obtain opacity or the big porous layer of whiteness.And improve the mouldability of porous layer.Pass through bag It is at least one kind of in calcium carbonate and titanium oxide, obtain the better porous layer.
Inorganic fine powder can implement hydrophily before being mixed with thermoplastic resin on the surface of inorganic fine powder Processing or hydrophobicity processing.Can be many by implementing hydrophily processing or hydrophobicity processing on the surface of inorganic fine powder Hole matter layer assigns the various properties such as printing adaptability, coating adaptability, resistance to nuzzling up property, secondary operation adaptability.At surface Reason agent is enumerated：The organic carboxyl acids such as aliphatic acid, aromatic carboxylic acid, resin acid and their salt, ester or acid amides；Organic sulfonic acid and its Metal salt；Silane coupler；Silicone oil；Phosphate；Include the polymer of carboxyl, secondary amino group~tertiary amino or quaternary ammonium salt.At these It is also preferred that using in surface conditioning agent：Oleic acid, maleic acid, stearic acid and their ester or acid amides or, wrap carboxylic polymer Or the polymer comprising quaternary ammonium salt.
Enumerated as above-mentioned organic carboxyl acid：Caproic acid, octanoic acid, capric acid, laurate, myristic acid, palmitic acid, stearic acid, flower The saturated fatty acids such as raw acid, behenic acids, lignoceric acid；Sorbic acid, elaidic acid, palmitoleic acid, oleic acid, linoleic acid, leukotrienes, The unrighted acids such as cetoleic acid, erucic acid, castor oil acid, maleic acid；The aromatic series such as benzoic acid, phthalic acid, naphthoic acid Carboxylic acid；The resin acids such as biotin acid, pimaric acid, palmitoleic acid.The salt of above-mentioned organic carboxyl acid can be：The sodium of above-mentioned organic carboxyl acid Salt, sylvite, magnesium salts, aluminium salt, calcium salt, zinc salt, tin (IV) salt, ammonium salt, diethanolamine salt etc..
Enumerated as the ester of above-mentioned organic carboxyl acid：Ethyl ester, vinyl esters, diisopropyl ester, cetyl, octyl group ester, tristearin Ester etc..Enumerated as the acid amides of above-mentioned organic carboxyl acid：Acid amides monooctyl ester, stearmide etc..
Enumerated as above-mentioned organic sulfonic acid：Include lauryl, myristyl, palmityl, stearyl, oil base, cetyl etc. The alkylsurfuric acid of alkyl；The aromatic sulphonic acids such as naphthalene sulfonic acids, DBSA；Sulfosuccinic acid, dioctyl sodium sulfosuccinates acid, The carboxylic sulfonic acid such as lauryl sulfoacetate, tetradecene sulfonic acid；Polyoxyethylene lauryl ether sulfuric acid, ethylene nonyl benzene The polyoxyethylene alkyl ether sulfuric acid such as base ether sulfuric acid.The salt of above-mentioned organic sulfonic acid can be：Lithium salts, sylvite, sylvite, magnesium salts, calcium salt, Zinc salt, aluminium salt, tin (IV) salt, ammonium salt etc..
Enumerated as above-mentioned silane coupler：3- r-chloropropyl trimethoxyl silanes, vinyltrimethoxy silane, vinyl Triethoxysilane, vinyl three (2- methoxy ethoxies) silane, 3- methacryloxypropyl trimethoxy silanes, 3- Glycidylpropyl trimethoxy silane, 3-mercaptopropyi trimethoxy silane, 3- aminopropyl triethoxysilanes etc..As Above-mentioned silicone oil is enumerated：Dimethicone, methylhydrogenpolysi,oxane, methyl phenyl silicone oil, cyclic dimethyl polysiloxane, Yi Jiyou The modified silicone oil such as alkyl, polyethers, alcohol, fluorine, amino, sulfydryl, epoxy radicals, higher fatty acids.
Enumerated as above-mentioned phosphate：Trimethyl phosphate, triethyl phosphate, tributyl phosphate, ethylhexyl dihydrogen phosphate, Triphenyl phosphate, 2- ethylhexyl diphenyl phosphates, resorcinol diphenol phosphate, double-ethylhexyl dihydrogen phosphate, phosphoric acid Diiso decyl ester, 2- methacryloxyethyls phosphate ester acid, methyl phosphate ester acid, butyl acid phosphate, phosphoric acid Mono-n-butylester, 2- butyl hexyls phosphate ester acid, polyoxyethylene lauryl ether phosphoric acid.As including above-mentioned carboxyl, secondary amino group~uncle The polymer of amino or quaternary ammonium salt is enumerated：Assign carboxyl, the monomer of secondary amino group~tertiary amino or quaternary ammonium salt with can be anti-with the monomer The copolymer for the single amount body answered makes 4 grades of agents and polymer obtained from the polymer reaction comprising secondary amino group~tertiary amino.
The usage amount of surface conditioning agent is more than 0.01 mass parts, more preferably with respect to the mass parts of inorganic fine powder 100 It is more than preferably 0.1 mass parts.So as to for example improve the dispersiveness of inorganic fine powder.The preferred phase of usage amount of surface conditioning agent It is below 10 mass parts, below more preferably 5 mass parts for the mass parts of inorganic fine powder 100.So as to for example be had Enough printings or the porous layer of in-molded adaptability.
The content of inorganic fine powder in porous layer can be relative to porous layer generally more than 35 mass %.It is many The emptying aperture of hole matter layer is mainly what is formed when stretching the resin containing inorganic fine powder around inorganic fine powder.Cause This, the emptying aperture quantity in porous layer can be increased by increasing the content of the inorganic fine powder in porous layer.So as to carry The thermal insulation of high porous layer.Further, since the quantity increase of the emptying aperture wall in porous layer, therefore be not easy when in-molded Cause the distortion of porous layer.The content of inorganic fine powder in porous layer can be relative to porous layer generally 40 matter Measure more than %, preferably more than 45 mass %.
The content of inorganic fine powder in porous layer can be relative to porous layer generally below 75 mass %.From And heat can be suppressed and spread by inorganic fine powder, the thermal conductivity excessive descent of porous layer.Obtain having stretching enough The porous layer of characteristic.The content of inorganic fine powder in porous layer can be relative to porous layer generally 70 mass % Hereinafter, preferably below 65 mass %.
In addition, the content of the inorganic fine powder in porous layer passes through JIS P 8251:2003 " paper, paperboard and paper pulp The measure of -525 DEG C of combustion methods of ash content method of testing " is determined.In addition, implementing when on the surface of inorganic fine powder at hydrophily When reason or hydrophobicity processing, the content of the inorganic fine powder in porous layer is with the matter of the inorganic fine powder before being surface-treated Calculated on the basis of amount.The quality of the surface conditioning agent used when inorganic fine powder is surface-treated is used as aftermentioned additive (example Be such as dispersant or lubricant) quality treatment.
The volume average particle size determined by laser diffractometry of inorganic fine powder is preferably more than 0.1 μm, more preferably More than 0.3 μm.So as to have the porous layer of enough thermal insulations when obtaining utilizing as in-mold shaping label.
The volume average particle size of inorganic fine powder is preferably less than 10 μm, preferably less than 4 μm.It is many so as to increase The quantity of emptying aperture in the matter layer of hole.Also improve the outward appearance on thermoplastic resin membrane surface.For example, the volume of inorganic fine powder is put down When equal particle diameter is less than 4 μm, the bumps of film surface diminish, and when being printed to film surface, printer's ink is equably shifted, Be improved the effect of print quality.
The average grain diameter of inorganic fine powder is smaller, and the quantity of the emptying aperture in porous layer more increases.Therefore it is inorganic micro- The smaller average grain diameter of fine powder is preferred.Even if however, the average grain diameter very little of inorganic fine powder, if inorganic micro- Big particle is included in fine powder, then the emptying aperture wall in porous layer is thinning, or emptying aperture connection, make under the intensity of porous layer Drop, easily distortion.Therefore, JIS standard screen (JIS Z 8801-1 of the inorganic fine powder in 45 μm of mesh:2006 " test sieves 1, net-the：Metal mesh screen net ") in residual quantity be preferably residual quantity in below 5ppm, the JIS standard screens of 38 μm of mesh More preferably below 5ppm.
In addition, the D50 and D90 of inorganic fine powder can meet the relational expression of 1.2≤D90/D50≤2.1.D50 serves as reasons The particle diameter of accumulation 50% for the volume reference that laser diffractometry is determined, referred to as median particle diameter.D90 is the body determined by laser diffractometry The particle diameter of accumulation 90% of product benchmark.The tangerine that can suppress to be produced by the distortion of porous layer by using this inorganic fine powder Skin phenomenon.
Residual quantity in the JIS standard screens of 45 μm of mesh meets the sharp keen of above-mentioned relation for below 5ppm or D50 and D90 The inorganic fine powder of size distribution obtained by improving effectiveness of classification.Enumerated as this inorganic fine powder：CUBE- 13B (Marno Calcium Co., Ltd.'s system), CUBE-06B (Marno Calcium Co., Ltd.'s system), BF-100 (standby north efflorescence Industrial Co., Ltd System) etc..
As described above, at least one of content and particle diameter by adjusting inorganic fine powder, and with existing heat Plastic resin is compared for the in-mold shaping label of porous film of main component, and the size for obtaining emptying aperture is small, emptying aperture footpath point Cloth is narrow, the porous layer more than emptying aperture quantity.Porous film using existing thermoplastic resin as main component passes through to shaping Stretched and be made with high magnification for the thermoplastic resin of sheet.Therefore, it is difficult to be formed as the such emptying aperture size of present embodiment Small, empty pore-size distribution is narrow, the porous layer more than emptying aperture quantity.
Emptying aperture size in porous layer is for example expressed as the surface of inorganic fine powder and the ultimate range to emptying aperture wall. The surface of inorganic fine powder can be less than 50 μm with the ultimate range to emptying aperture wall.So as to more effectively suppress in mould The distortion of porous layer during shaping.
The surface of inorganic fine powder is with the ultimate range electron microscope to emptying aperture wall to film or porous layer Section is observed, and is determined by the image analysis of section picture.Specifically, by film with after epoxy resin parcel solidification, with cutting The abreast cutting (i.e. perpendicular with face direction) of thickness direction of the piece machine along such as film.To cutting after cross section metal spraying plating, with sweeping Any multiplying power (such as 500 times~2000 times) that type electron microscope is retouched to be easy to observation is amplified shooting.Will be resulting Image reading carries out image procossing into image analysis apparatus, determine the surface of inorganic fine powder with to emptying aperture wall it is maximum away from From.
(additive)
Enumerated as the additive included in porous layer：Dispersant or lubricant, heat stabilizer, light stabilizer, anti-band Electric agent etc..Total 100 mass parts of the content of additive in porous layer relative to thermoplastic resin and inorganic fine powder Can be 0.1~5 mass parts.Obtain the excellent porous layer of time stability.
When porous layer contains dispersant or lubricant, the content of dispersant or lubricant in porous layer relative to Total 100 mass parts of thermoplastic resin and inorganic fine powder are preferably more than 0.1 mass parts.So as to fully find The function of dispersant or lubricant.The content of dispersant or lubricant in porous layer is relative to thermoplastic resin and inorganic micro- Total 100 mass parts of fine powder are preferably below 4 mass parts, below more preferably 2 mass parts.So as to obtain mouldability, print The excellent porous layer such as brush adaptability.Enumerated as dispersant or lubricant：From silane coupler；The carbon such as oleic acid and stearic acid Aliphatic acid and its metal salt, acid amides, the ester with the alcohol of carbon number 1~6 of number 8~24；Poly- (methyl) acrylic acid and its metal salt etc. Selected in the group of composition more than one.
When porous layer contains heat stabilizer, the content of dispersant or lubricant in porous layer is relative to thermoplasticity Total 100 mass parts of resin and inorganic fine powder are preferably more than 0.001 mass parts.So as to fully find heat stabilizer Function.Total 100 of the content of dispersant or lubricant in porous layer relative to thermoplastic resin and inorganic fine powder Mass parts are preferably below 1 mass parts, below more preferably 0.5 mass parts.So as to obtain the porous layer of economical.Separately Outside, enumerated as the heat stabilizer for the outward appearance for improving thermoplastic resin membrane：From the heat stabilizer such as Hinered phenols, Phosphorus, amine Selected in the group that (otherwise referred to as antioxidant) is constituted more than one.
When porous layer contains light stabilizer, the content of dispersant or lubricant in porous layer is relative to thermoplasticity Total 100 mass parts of resin and inorganic fine powder are preferably more than 0.001 mass parts.So as to fully find light stabilizer Function.The content of dispersant or lubricant in porous layer is total relative to thermoplastic resin and inorganic fine powder 100 mass parts are preferably below 1 mass parts, below more preferably 0.5 mass parts.So as to obtain the Porous of economical Layer.In addition, being enumerated as the light stabilizer for the outward appearance for improving thermoplastic resin membrane：From hindered amines, benzotriazole, hexichol The light stabilizers such as ketone class constitute group in select more than one.Light stabilizer can be used in combination with above-mentioned heat stabilizer.
[bonding layer]
In the present embodiment, film is attached on container body when by in-molded, bonding layer be arranged at Container body is in contact on the face of side.When by it is in-molded film is attached on container body when, the surface of bonding layer is melted Melt, film is attached on plastic containers by integrated with the molten resin of container body and cooling down.
Bonding layer preferably by using the fusing point thermoplastic resin lower than the fusing point of contained thermoplastic resin in porous layer as The resin combination of main component is constituted.As contained by the fusing point and porous layer of the thermoplastic resin of the main component of bonding layer The difference of the fusing point of resin combination is preferably more than 10 DEG C, more preferably more than 15 DEG C.So as to suppress film in past container The deformation of porous layer when being attached in main body.
It is used as the fusing point of resin combination contained by the fusing point and porous layer of the thermoplastic resin of the main component of bonding layer Difference be preferably less than 150 DEG C.So as to suppress the film blocking that film attaches the process last stage, it is easily processed film. The last stage for attaching process as film enumerates：Keeping stage, process segment of film of film etc..
Enumerated as the thermoplastic resin used in bonding layer：Gather from the high-pressure process of extremely-low density, low-density or Midst density Ethene, straight chain wire low density polyethylene (LDPE), ethylene vinyl acetate copolymer, ethylene acrylic acid co polymer, the carbon of alkyl The ethylene alkyl methacrylate that ethylene alkyl acrylate polymer that number is 1~8, the carbon number of alkyl are 1~8 is total to Propylene resin, polyester resin, styrenic elastomer resin, polyamide representated by polymers, propylene alpha olefin copolymer Selected in the group of the compositions such as resinoid more than one.Bonding layer can comprising straight-chain low density polyethylene (LDPE) as mainly into Point.So as to obtain the bonding layer of heat-sealing engagement good strength.
Bonding layer can include other known resin additives in the range of without prejudice to heat sealability.It is used as other trees Fat additive can be enumerated：Inorganic pigment, dyestuff, core agent, plasticizer, releasing agent, incombustible agent, antioxidant, light stabilizer, Ultra-violet absorber etc..The addition of other resin additives is preferably with respect to bonding layer generally below 10 mass %, more Preferably below 5 mass %.So as to suppress the phenomenon that film accumulates additive in continuous manufacture on die head.
The manufacture method of film with bonding layer is not specially limited, and is fed for example with being used in extrusion molding The method of the multilayer die head mode of block, branch manifold etc.；Using multiple die heads, extruded layer folds the side of bonding layer on porous layer Formula；Combination of these methods etc..Can be by setting bonding layer on the porous layer of coating process after shaping.
When setting bonding layer by coating process, according to an embodiment, the above-mentioned material for constituting bonding layer is melted In organic solvent, it is dried afterwards in the one side for be coated on porous layer.According to another embodiment, structure will be included Water-base resin latex into the above-mentioned material of bonding layer is coated in the one side of porous layer.
Above-mentioned water-base resin latex is for example according to Japanese Unexamined Patent Application 58-118843, Japanese Unexamined Patent Application No. 56-2149, day The method of the record such as this JP 56-106940 and Japanese Unexamined Patent Application 56-157445 publications is obtained.Specifically, first to The material (otherwise referred to as bonding layer materials) that the supply of two axle screw extruders constitutes bonding layer carries out mixing melting.Hereafter, by The liquid ingress pipe of the compressional zone or delivery area that are arranged at extruder imports the water containing dispersion liquid, is made by rotating screw rod The copolymer resin of melting is kneaded with water.Then, so as to get mixture extruding casing in counter-rotating, from going out for extruder Mouth mouth is discharged into atmospheric pressure region, is further added water, is contained in storage tank as needed.
The average grain diameter of bonding layer materials in water-base resin latex is preferably 0.01~3 μm, more preferably 0.1~1 μm. When olefine kind resin particle average grain diameter within the above range when, in the state of dispersion liquid mutually stablize, the keeping of liquid And screening characteristics is excellent.Resulting film is attached in addition, applying bonding layer formed by the dispersion liquid by in-molded After on bottle, i.e., in the state of synthetic resin, the transparency is intended to further optimization.In order that average grain diameter is located at Above range, can be added for making the scattered dispersant (for example, various surfactants) of bonding layer materials.
The average grain diameter of bonding layer materials in water-base resin latex is calculated as follows.First, in low temperature and decompression Under the conditions of make sample solution (such as olefine kind resin latex solution) dry.With scanning electron microscope with the multiplying power of appropriateness (such as 1,000 times) are by the dried sample bust shot photograph image.Calculated and existed in the sample according to the image of shooting Elective 100 particle diameters (major diameter) average value.Average grain diameter is calculated accordingly.
The solid component concentration of bonding layer materials in water-base resin latex is preferably 8~60 mass %, more preferably 20 ~50 mass %.If the solid component concentration is within the above range, in the state of dispersion liquid mutually stablize, the guarantor of liquid Pipe and screening characteristics are also excellent.
[superficial layer]
Superficial layer can be Porous, may not be Porous.When the overprinting information on superficial layer, superficial layer Preferably Porous.So as to improve the adaptation of superficial layer and printing ink.
The resin for constituting superficial layer can be resinous to be of the same race with porous layer institute, or xenogenesis.It is used as composition table The resin of surface layer is enumerated：From propylene resin, high density polyethylene (HDPE), medium density polyethylene, straight chain wire low density polyethylene (LDPE), α- Olefinic copolymer, ethylene vinyl acetate copolymer, ethylene acrylic acid co polymer, ethylene alkyl acrylate copolymerization Thing, ethylene alkyl methacrylate copolymer (carbon number of alkyl is 1~8), the gold of ethylene methacrylic acid copolymer Belong to the polyolefin resins such as salt, poly(4-methyl-1-pentene), ethylene-cyclic olefin copolymer；PLA, poly terephthalic acid second The polyester resins such as terephthalate resin, polycarbonate resin；Polyvinylchloride-based resin；Nylon-6, nylon-6,6, nylon-6, 10th, nylon-6,12 grade polyamide-based resins；ABS resin；Ethylene methacrylic acid copolymer metal salt (Zn, Al, Li, K, Na etc.) etc. ionomer resin constitute group in select more than one.
Constitute thermoplastic resin of the resin preferably fusing point of superficial layer for 105~280 DEG C of scopes.Fusing point is 105~280 DEG C The thermoplastic resin of scope can be selected from propylene resin, high density polyethylene (HDPE), pet resin etc. Select.Fusing point can include resin of more than two kinds for the thermoplastic resin of 105~280 DEG C of scopes.The resin for constituting superficial layer can be with It is main component comprising propylene resin or high density polyethylene (HDPE).It is excellent so as to obtain water resistance, chemical reagent resistance, economy etc. Good superficial layer.
Constituting the resin of superficial layer can be：With the high polyamide-based resin of compatibility of printing ink, ionomer resin, The high resin of PLA, polycarbonate resin isopolarity.In addition, constituting the resin of superficial layer can include：Polyamide-based tree Fat, ionomer resin, PLA, polycarbonate resin isopolarity high resin and polypropylene-based resin, high-density polyethylene The low resin of alkene, pet resin isopolarity.
Superficial layer can also include inorganic fine powder.In one embodiment, contain in superficial layer relative to surface The thermoplastic resin of layer is 5~45 mass % inorganic fine powder, and the inorganic fine powder is calcium carbonate, talcum, oxidation Titanium etc. and volume average particle size are 0.1~3 μm.So as to obtain the superficial layer for being adapted to printing adaptability.And film can be improved Whiteness and at least one of opacity.In another embodiment, superficial layer contains the heat relative to superficial layer Plastic resin is 0.1~3 mass % inorganic fine powder, and the inorganic fine powder is calcium carbonate, silica, aluminum oxide Deng and volume average particle size is 3~10 μm of inorganic fine powder.It is concavo-convex so as to be assigned for superficial layer.As a result had The superficial layer of resistance to blocking.By suppressing the content of the inorganic fine powder in superficial layer, film can be suppressed and continuously manufactured When on die head accumulate additive phenomenon.
Superficial layer can include anti-live agent.Enumerated as anti-live agent：" the ぺ レ of Sanyo Chemical Industries, Ltd. ス タ Star ト " (trade name), " エ レ U Application PE200 " etc. of Dainichiseika Color Chem.
The content of anti-live agent in superficial layer is 0.1 matter preferably with respect to the mass parts of thermoplastic resin 100 of superficial layer Measure more than part, more than more preferably 0.5 mass parts.When superficial layer includes inorganic fine powder, the anti-live agent in superficial layer Content relative to the thermoplastic resin of superficial layer and total 100 mass parts of inorganic fine powder be preferably 0.1 mass parts with On, it is more than more preferably 0.5 mass parts.So as to fully find anti-charging property.
The content of anti-live agent in superficial layer is preferably 3 mass relative to the mass parts of thermoplastic resin 100 of superficial layer Below part, below more preferably 2 mass parts.When superficial layer includes inorganic fine powder, anti-live agent in superficial layer contains Measure and be preferably below 3 mass parts relative to the thermoplastic resin of superficial layer and total 100 mass parts of inorganic fine powder, it is more excellent Elect as below 2 mass parts.So as to suppress turn of the printer's ink caused by surface movement of the anti-live agent to superficial layer Move bad, closely sealed bad, mold fouling etc..
Superficial layer can be included with that can be added to the additive identical additive of porous layer.Additive in superficial layer As long as content for the characteristics such as the transparency required by without prejudice to film, flexibility, rigidity scope, for example, relative to The thermoplastic resin of superficial layer is 0.01~3 mass %, more preferably preferably 0.01~2 mass %, 0.01~1 mass %. By suppressing the content of the additive in superficial layer, film can be suppressed showing for additive is accumulated on die head in continuous manufacture As.
The manufacture method of film with superficial layer is not limited to this, can use and the film identical with bonding layer Gimmick is manufactured.For example, can be extruded and manufactured from die head by superficial layer by the shaping with porous layer simultaneously, it can also use Multiple die heads are manufactured by extruding stacking superficial layer on porous layer, can also pass through the superficial layer by film-form is shaped to Fit on porous layer to manufacture.
[surface coating layer]
In one embodiment, for improve printer's ink or the various functions material layer formed in post-processing process with it is thin The adaptation of film and form surface coating layer.In other embodiments, to improve the bond strength of container body and film Form surface coating layer.Surface coating layer can include zygosity material.Surface coating layer can include anti-live agent, additive Deng.
(zygosity material)
Zygosity material improves the zygosity of surface coating layer and film surface.In addition, regulation film surface is used with printing The engagement of ink or various functions material layer.Enumerated as zygosity material：Water-soluble polymer, aqueous dispersion polymerization thing (have When be also referred to as latex) etc..Vinyl group resin latex or polyurethane resin latex can be enumerated as aqueous dispersion polymerization thing.
Water-soluble polymer preferably has following property：(it is sometimes referred to as comprising the material for constituting surface coating layer For surface coating layer material) coating agent in be dissolved in water, the coating agent is coated on film surface, but will not be redissolved after drying Yu Shui.Material for bonding layer is heated melting or softening can show adhesion, but the zygosity material in surface coating layer It is preferred that even if can also show at room temperature adhesion.
Enumerated as water-soluble polymer：The vinyl-based copolymers such as PVP；Partly-hydrolysed poly- second Enol (otherwise referred to as PVA), fully saponified PVA, the salt of isobutyiene-maieic anhydride copolymer (can for example exemplify alkali Metal salt, ammonium salt etc.) vinyl-based copolymer hydrolysate；(the first such as poly- (methyl) PAA, poly- (methyl) acrylamide Base) acrylic acid derivative；Modified polyamide；The cellulose derivatives such as carboxymethyl cellulose, carboxyethyl cellulose；Polyethyleneimine The ring-opening polymerisation such as amine, polyethylene oxide, polyethylene glycol family macromolecule or these modifier；The natural class such as gelatin, starch are high Molecule or these modifier etc..Preferably use among these partly-hydrolysed PVA, fully saponified PVA, polyethyleneimine, Polyethyleneimine-modified thing.Water-soluble polymer preferably comprises the carbodiimide class that can be reacted and be crosslinked with water-soluble polymer； Diisocyanates；2-glycidyl ethers etc. is 1~200 mass parts relative to the mass parts of water-soluble polymer 100.
Constituting the vinyl monomer of vinyl based copolymer can be：From olefines；Vinyl ester；Unsaturated carboxylic acid Class and their alkali metal salt or acid anhydrides；The ester of the alkyl with branch or cyclic structure of the carbon number untill 12；(methyl) third Acrylamide, while having the derivative of the alkyl of carbon number 1~4 and the alkylidene of carbon number 1 or 2；And dimethyldiallylammonium Salt constitute group in select more than one.In addition, above-mentioned salt is preferably：Sour residue and for methyl sulfate ion, chloride from Son.
(anti-live agent)
Anti-live agent suppresses by powered caused failure.Anti-live agent can be to have being total to for quaternary ammonium salt structure in intramolecular Polymers.So as to prevent powered and without prejudice to surface coating layer and ink or various functions material layer zygosity.In a reality Apply in mode, there is the copolymer of quaternary ammonium salt structure by using the monomer with tertiary amine structure as neccessary composition in intramolecular, Obtain can with after the copolymer of the monomer of its copolymerization, to the tertiary amine dimethyl sulfate, the chloro- 2- Hydroxyproyl Trimethyls chlorinations of 3- 4 grades of agents such as ammonium, glycidyltrimetiiylammonium ammonium chloride carry out 4 grades and change and obtain.
In another embodiment, there is the copolymer of quaternary ammonium salt structure in intramolecular using only unazotized monomer Obtain after copolymer, obtained by being grafted the monomer with quaternary ammonium salt structure.Pass through the hydrophilic of quaternary ammonium salt structure and copolymer The balance of the amount of base and the amount of hydrophobicity base, the copolymer in intramolecular with quaternary ammonium salt structure can be designed to it is water-soluble, Any one in aqueous dispersion, organic solvent-soluble, therefore, it is possible to the solvent of the coating corresponding to manufacture surface coating layer Suitably selected.
Further, in another embodiment, the vinyl group resin latex or poly- as zygosity material is constituted The monomer of urethane resin emulsion can use the monomer with quaternary ammonium salt structure, so as to obtain having quaternary ammonium salt structure in intramolecular Vinyl group resin latex or polyurethane resin latex, can also using with tertiary amine structure monomer obtain latex it Afterwards, 4 grades of changes are carried out by using 4 grades of agents and obtains above-mentioned latex.
Anti-live agent can also be cationic metal oxide sol.Cationic metal oxide sol can be oxygen Change Alumina gel, alumina-coated silicon dioxide gel.Enumerated as the manufacture method of alumina sol：By alkoxide such as aluminium isopropoxides The method (i.e. so-called sol-gal process) that is hydrolyzed and is manufactured with acid, it will be closed in the flame of aluminium chloride importing hydrogen etc. Into method (i.e. so-called vapor phase method) etc..Enumerated as the manufacture method of alumina-coated silicon dioxide gel：By by four Method that the alkoxides such as Ethoxysilane are hydrolyzed and manufactured with acid, silicon tetrachloride is imported into the flame of hydrogen etc. carried out The method of synthesis, method etc. that waterglass spent ion exchange resin is carried out into desalination obtain making chlorination after silicon dioxide gel The method of aluminium, acetylacetone,2,4-pentanedione reactive aluminum.
<The manufacture method of film>
The film of present embodiment can use known porous film autofrettage manufacture.The film of present embodiment is excellent Elect as along the film that at least 1 direction of principal axis is stretched.
[shaping]
The shaping of film is preferred to use extrusion moulding.In addition, the method for the description below also can be suitably used for film by least 1 The situation that layer porous layer is constituted, also can be suitably used for film also has bonding layer, superficial layer etc. on the basis of porous layer Situation.
Enumerated as extrusion moulding：Sheetmolding method, blow molding method, rolling-molding method, calendering formation etc..Sheetmolding method For example, pass through the fusing point for being set as the thermoplastic resin than constituting film or the extruding of the higher temperature of glass transition temperature Film raw material is kneaded and melted by machine, and sheet is extruded as using T moulds, I moulds etc., is carried out by metallic roll, rubber rollers, metal tape etc. cold But so that the method for the synthetic resin of film-form is made.Blow molding method is, for example, that will use circle by the raw material of mixing melting Mould is extruded into tubulose, and it is expanded with predetermined multiplying power by overpressure, while it is thin so as to be made to carry out cooling by empty gas and water etc. The method of membranaceous synthetic resin.Rolling-molding method is, for example, that the material kneaded is carried out into calendering with multiple hot-rollings to be processed into Sheet is so as to the method that resins in film form products formed is made.
In one embodiment, film is molded by cast-forming method.Cast-forming method is, for example, by the heat of composition film Thermoplastic resin composition is supplied to extruder to be melted, and is extruded as sheet using the T moulds connected on extruder and is pressed on cold But cooling is carried out on roller so as to the method that resins in film form products formed is made.
The film of sandwich construction can be made according to known method.Enumerated as the method for manufacture multilayer films：Make With the multilayer die head mode of feed block, branch manifold etc.；Use the extruding overlapped way of multiple die heads；And their combination.
In one embodiment, one layer in cast-forming method molding thermoplastic resin film is passed through.As needed, it is sharp After being stretched with roller difference to the layer obtained by cast-forming method, by melt lamination be used for constitute film other The resin combination of layer and obtain the layered product of sandwich construction.
[stretching]
When stretching is used to constitute any layer of film, drawing process is not particularly limited, and can be used known various Method.Specifically, the stretching of each layer can also be the stretching of 1 axle, the stretching of 2 axles, tensionless winkler foundation.Moreover, draw direction can also be vertical Direction, transverse direction.Further, when being stretched for 2 axles, it can simultaneously stretch, can also gradually stretch.
As drawing process, enumerated when stretching casting film：Using the vertical pulling method of the difference of roller group, Biaxially stretched method etc. simultaneously using the horizontal pulling method of Tenter oven, rolling process, by the combination of Tenter oven and linear electric machine.Separately Outside, Biaxially stretched method while based on tubulose method is enumerated when stretch-blow film.
The condition of film of the stretching comprising porous layer is preferably low range.So as to form fine emptying aperture.Present dynasty's folk prescription To during stretching, stretching ratio is preferably about 1.2~8 times, more preferably 2~5 times.When for it is Biaxially stretched when, stretching ratio is with face Product dynameter is preferably 1.5~12 times, more preferably 2~6 times.It is too low so as to suppress stretching ratio, it is impossible to obtain emptying aperture Or emptying aperture skewness.
Draft temperature is set in the temperature range for being suitable for thermoplastic resin contained by porous layer.In an embodiment In, draft temperature is set to the temperature more than glass transition temperature temperature and below the fusing point of crystallization unit.Draft temperature is excellent Elect 1~70 DEG C lower than fusing point of temperature as.When the main component of the thermoplastic resin included in porous layer is Noblen When (155~167 DEG C of fusing point), draft temperature is preferably 100~164 DEG C.As the master of the thermoplastic resin included in porous layer When wanting composition for high density polyethylene (HDPE) (121~134 DEG C of fusing point), draft temperature is preferably 70~133 DEG C.When bag in porous layer When the main component of the thermoplastic resin contained is polyethylene terephthalate (246~252 DEG C of fusing point), draft temperature is preferred For the temperature that will not be intensely crystallized.
Draw speed is preferably 1~350m/ points, more preferably 5~150m/ points.Additionally, it is preferred that implementing after the stretch at heat Reason.The temperature of heat treatment is preferably more than draft temperature and below 30 DEG C higher than draft temperature of temperature.By implementing heat treatment, Ripple caused by contraction when can suppress winding, hot and molten disconnected envelope when percent thermal shrinkage reduction, the product keeping as draw direction Deng.Heat treatment can be implemented using at least one of roller and hot stove.The film of stretching is preferably being kept what is tightened by heat treatment Carried out under state.So as to effectively implement heat treatment.
[surface treatment]
(oxidation processes)
Oxidation processes can be implemented in film surface.The surface free energy of film surface after shaping, than relatively low, is hydrophobic Property have and be easy to ink and the trend that flicks of coating agent.By implementing oxidation processes to film surface, it is possible to increase film surface Surface free energy.So as to improve printer's ink and post-processing process formation various functions material layer (for example, sensible heat chromonic layer, Ink-jet houses layer, cement layers, dry lamination layer) at least one of adaptation with film.
In the face (sometimes referred to as pellicular front or film surface) perpendicular with thickness direction of film, by in-molded It can implement oxidation processes in the face for the side that is in contact with molten resin when film is attached at into container body.Specifically, when thin When film has bonding layer, oxidation processes are implemented on the face that the bonding layer side of porous layer is configured with pellicular front.Work as engagement When layer is configured at the outermost of film, oxidation processes are implemented to bonding layer.In addition, when film without bonding layer with surface During layer, oxidation processes are implemented on the face that the side of the superficial layer of porous layer is not provided with pellicular front.It is thin so as to improve The bond strength of film and container body.
It can be enumerated as surface oxidation treatment：Corona discharge Treatment, flame treatment, corona treatment, glow discharge Processing, ozone processing etc..Corona discharge Treatment, corona treatment are preferably used as surface oxidation treatment.
When for Corona discharge Treatment, oxidation processes amount is preferably 10W points/m2(600J/m2) more than, more preferably 20W points/m2(1,200J/m2) more than.So as to show enough effects.When for Corona discharge Treatment, oxidation processes amount is excellent Elect 200W points/m as2(12,000J/m2) below, more preferably 180W points/m2(10,800J/m2) below.So as to press down The adaptation that system is handled and caused with over oxidation declines.
(coating)
When implementing oxidation processes in film surface, surface free energy declines with the time sometimes, reduces adaptation.Cause This, preferably implements working procedure of coating to form table in 1 week after surface oxidation treatment is just carried out or from surface oxidation treatment Face overlay.Enumerated as coating method：By die coating machine, roll coater, gravure apply machine, flush coater, blade apply machine, inversely apply machine, The coating of the progress such as gas knife, size press painting machine, impregnating.
Coated technique both can in the forming production line of film with film forming common implementing, can also with film Coated technique is implemented to the film being molded on the forming production line in the separated production line of forming production line.When porous layer into When type is pulling method, it can both implement working procedure of coating before stretching process, working procedure of coating can also be implemented after stretching process.Apply Can be as needed through removing excess of solvent using the drying process of drying oven etc., so as to form surface coating after deposited process Layer.
If the thickness of surface coating layer is blocked up, the solidifying of surface coating layer composition can be caused in the inside of surface coating layer Knot.So as to which the adaptation of film and ink or function material layer coating liquid can be caused to decline.Therefore, applied toward the surface applied on film The upper limit of the coating amount of coating is preferably 20g/m with solid state component conversion after the drying of per unit area (square metre)2, more preferably For 5g/m2, most preferably 1g/m2。
On the other hand, if the thickness of surface coating layer is excessively thin, the composition of surface coating layer cannot be uniformly present in The surface of film, so as to be difficult to obtain enough surface treatment effects, the adaptation of film and ink or function material layer coating liquid Decline.Therefore, the lower limit of coating amount is preferably 0.07g/m2, more preferably 0.1g/m2, most preferably 0.15g/m2。
The coating amount of surface coating layer is determined according to following step.First, from just on film apply coating agent it Film quality before coating coating agent is subtracted in wet film quality afterwards calculates wet coating amount.Coating is multiplied by wet coating amount The solid component concentration of agent with determine solid state component conversion coating amount.But in the case of unavoidable, surface can also be applied Coating is peeled off from film, and dried coating amount is directly determined by measuring the quality for the surface coating layer being stripped.In addition, Can the section parallel with the thickness direction of film with scanning electron microscope pair observed to determine surface coating layer Thickness, the density of coating agent solid state component is multiplied by the thickness of surface coating layer to calculate dried coating amount.
Surface coating layer can be formed at least one side of film.In the face of film, the side only in printing information Or form surface coating layer being coated with by post-processing on the side of various functions material.In the face of film, pass through mould Interior shaping and on container body during adhered film, surface coating can also be only formed in the side that is in contact with molten resin Layer.
(Embossing processing)
When the film of the present invention is attached on plastic containers by in-molded, preferably make film and plastic containers The face reduction smoothness being in contact.Therefore, it is possible to carry out Embossing processing.Embossing processing uses the rubber paired with engraving metallic roll Roller.Embossing processing can both be carried out before the stretching in thin film fabrication, can also be carried out after the stretch.In addition, by by advance Having carried out the film adhered method on porous layer of Embossing processing can obtain being embossed the bonding layer of processing.
The pattern of Embossing processing is preferably to have continuous ditch obtained from the dandy roll of discontinuous recess has been carved in use Pattern and with 50~300 bar ditch dandy roll obtained from crest line pattern.
<The characteristic of film>
[characteristic of film flood]
(thickness)
The thickness D of film is according to JIS K 7130:1999 " plastic film and piece-thickness measuring methods " are thick using level pressure Analyzer is spent to determine.The thickness D of film is preferably more than 20 μm, more preferably more than 40 μm, more preferably 60 μm with On.Accordingly, by it is in-molded film is attached on container body when, using label inserter mould inner side insert During film, it is easy to which film is configured at into appropriate location.And the generation of film wrinkle can be suppressed.
The thickness D of film is preferably less than 250 μm, more preferably less than 200 μm.So as to suppress film and container master Space or container body between body produce frivolous part.So as to improve the resistance to drop strength of products formed.It can also reduce The processing cost of mould.
(density)
The density of film is based on JIS K 7112 by using film sample:1999 " density of plastics-non-foamed plastics and The A methods of the assay method of proportion " are determined according to displacement method in water.When film is only made up of porous layer, the density of film Preferably 0.5g/cm3More than, more preferably 0.6g/cm3More than.So as to keep the surface strength of label.In addition, film Density is preferably 1.3g/cm3Hereinafter, more preferably 1.0g/cm3Below.So as to assign IML zygosities for film, (heat-sealing is strong Degree).
In addition, when film is only made up of porous layer, can be applicable as the preferred scope of the density of the film aftermentioned Preferred scope in the density of porous layer.When film is the sandwich construction comprising porous layer, the density of film is preferably 0.6g/cm3More than, more preferably 0.7g/cm3More than.In addition, the density of film is preferably 1.4g/cm3Hereinafter, more preferably 1.1g/cm3Below.
(thermal resistance value)
The thermal resistance value R of filmtUsing according to ISO 22007-3:2008 use thermal conductivity measuring machine (ai-Phase Co., Ltd. System, machine name：Ai-Phase Mobaile) and the film flood thermal conductivity λ and film flood thickness D of measure are counted according to following formula Calculate.
Rt=d × 10-6/λ
Wherein, RtFor film thermal resistance value [m2K/W], D is the flood thickness [μm] of film, and λ is the flood thermal conductivity of film [W/m·K]。
The thermal resistance value R of filmtPreferably 0.05m2More than K/W, more preferably 0.1m2More than K/W.So as to press down The heat that film is received from molten resin when in-molded is made to flow out to outside film.As a result, in the face of film The thermoplastic resin that the layer set on the face of side that is in contact with container body is included has carried out abundant melting, therefore, it is possible to suppress The generation of foaming.
The thermal resistance value R of filmtPreferably 0.25m2Below K/W, more preferably 0.20m2Below K/W.To improve film Thermal resistance value RtIt is accomplished by for example reducing the density of Porous, increases the void content or emptying aperture length of porous layer.It is thin by making The thermal resistance value R of filmtWithin the above range, thin film strength decline, the generation of orange peel effect can be suppressed.
[characteristic of porous layer]
(thickness)
The thickness d of porous layer in film is determined by following step.First, observed by scanning electron microscope The section parallel with the thickness direction of film, porous layer shared thickness in film thickness D is determined by image analysis Ratio.Identified ratio is multiplied by according to JIS K 7130:What 1999 " plastic film and piece-thickness measuring methods " were determined Film thickness D determines the thickness d of porous layer.
Porous layer thickness ratio shared in film thickness is preferably less than more than 10% 100%.So as to obtain every Hot excellent porous layer.It additionally is able to obtain whiteness or the big porous layer of opacity.The ratio is preferably 25% More than, more preferably more than 30%.
(density)
The density p of porous layer in film is based on JIS K 7112:1999 " the density and ratio of plastics-non-foamed plastics The A methods of weight assay method " are determined according to displacement method in water.In addition, using the film being attached on tape label plastic containers as Sample, it is determined that during the density p of contained porous layer in the film, the density p of the porous layer is determined by following step.It is first First, the film for including porous layer is taken out from tape label plastic containers by cutting etc..Then, by porous layer from taking-up Film is peeled off and obtains density measurement sample.Then, based on JIS K 7112:1999 " the density and ratio of plastics-non-foamed plastics The A methods of the assay method of weight " are determined according to displacement method in water by being measured to above-mentioned density measurement with the density of sample The density p of porous layer.
However, when porous layer can not be peeled off from film, the density p of porous layer is determined according to following step.It is first First, the section of the film taken out from tape label plastic containers is observed with scanning electron microscope, is determined by image analysis The body of the thermoplastic resin in porous layer, inorganic fine powder and emptying aperture (sometimes referred to as each portion of porous layer) in film Product ratio.As above-mentioned volume ratio, the area ratio using each portion in image can be substituted.Then, porous layer is made The volume ratio in each portion is multiplied by the density p that the Zhi Xiang Calais after the density in each portion determines porous layer.For example, by making thermoplasticity The volume ratio of resin is multiplied by value obtained by the density of thermoplastic resin, the volume ratio of inorganic fine powder is multiplied by inorganic microfine Value, the volume ratio of emptying aperture obtained by the density of powder are multiplied by value obtained by atmospheric density and are added, to determine the close of porous layer Spend ρ.
The density of the porous layer of film is preferably 0.5g/cm3More than, more preferably 0.6g/cm3More than.So as to tie up Hold the surface strength of label.And the generation of orange peel effect can be suppressed.The density of the porous layer of film is preferably 1.3g/ cm3Hereinafter, more preferably 1.0g/cm3Below.So as to assign IML zygosities or heat seal strength for porous layer.
(real density)
The real density ρ of porous layer in film0The porous layer peeled off from film will be made to be used as sample after carrying out thermal contraction Product, based on JIS K 7112:The A methods of 1999 " density and the assay method of proportion of plastics-non-foamed plastics " are put according in water Method is changed to determine.In addition, in the situation that the composition of the thermoplastic resin composition used in porous layer has been distinguished, can To replace above-mentioned sample with newly formed resin combination based on the composition.
In addition, when that can not peel off porous layer from film, the real density of porous layer is determined according to following steps ρ0.First, with the section of scanning electron microscope viewing film, by image analysis, in the porous layer in film Emptying aperture beyond each portion, it is determined that volume ratio when using the whole volume of the part in addition to emptying aperture in porous layer as 1 Rate.As above-mentioned volume ratio, can instead of using each portion in image area ratio.Then, removing in porous layer is made The volume ratio in each portion beyond emptying aperture is multiplied by the real density ρ that the Zhi Xiang Calais after the density in each portion determines porous layer0.Example Such as, when porous layer is made up of thermoplastic resin and inorganic fine powder, thermoplastic resin and inorganic fine powder are determined It is respective relative to thermoplastic resin and the volume ratio of the volume of inorganic fine powder.The volume ratio of thermoplastic resin is multiplied by The volume ratio of value and inorganic fine powder after the density of thermoplastic resin is multiplied by value obtained by the density of inorganic fine powder It is added, to determine the real density ρ of porous layer0。
The real density of porous layer is preferably 1.0g/cm3More than, more preferably 1.2g/cm3More than.With in porous layer Inorganic fine powder content increase, the real density of porous layer also becomes big.Inorganic fine powder is considered as having played sky Hole generates the function of core, and by making the big containing quantitative change of the inorganic fine powder in porous layer, the quantity of emptying aperture generation core also increases Plus.When emptying aperture generates the quantity increase of core, the emptying aperture quantity after stretching also increases, and improves the thermal insulation of porous layer.Its Result is to uprise in-molded zygosity.In addition, if the emptying aperture quantity increase after stretching, then under the density of porous layer Drop, obtains the in-mold shaping label of light weight.
The real density of porous layer is preferably 1.9g/cm3Hereinafter, more preferably 1.8g/cm3Below.When emptying aperture footpath is excessive, Sometimes emptying aperture wall is easily distorted, but by the way that the real density of porous layer is adjusted into above range, can be made many after stretching Emptying aperture footpath in the matter layer of hole, which is pre-adjusted, arrives proper range.So as to be adequately suppressed the generation of orange peel effect.
(void content)
The void content p [%] of porous layer is obtained by using density p obtained from said determination and by said determination The real density ρ arrived0Calculated by following formula.
P=(ρ0-ρ)/ρ0×100
The void content of porous layer can be more than 15%, preferably more than 25%, more preferably more than 35%.So as to To the excellent porous layer of thermal insulation.And obtain whiteness or the big porous layer of opacity.The void content of porous layer can Think less than 75%, preferably less than 70%, more preferably less than 65%.So as to suppress orange peel effect.
(emptying aperture length)
As the index for the emptying aperture amount for representing porous layer, the thickness based on above-mentioned void content and above-mentioned porous layer is utilized The emptying aperture length L that d is calculated by following formula.
L=d × (ρ0-ρ)/ρ0
Herein, L is emptying aperture length [μm], and ρ is the density [g/cm of porous layer3], ρ0For the real density [g/ of porous layer cm3]。
Emptying aperture length L is represents the index of emptying aperture proportion in porous layer thickness d, and emptying aperture length L is longer, shows Thermal insulation is higher.Preferably more than 20 μm of emptying aperture length L.Received so as to suppress the film when in-molded from molten resin Heat flow out to outside film.So as to improve the engaging force of film and container body.
[characteristic of bonding layer]
(thickness)
The thickness of bonding layer is determined by the step identical with the thickness d of porous layer.First, it is aobvious with scanning electron Micro mirror observes the section parallel with the thickness direction of film, determines the thickness of bonding layer in film thickness by image analysis Proportion in D.Identified ratio is multiplied by according to JIS K7130:1999 " plastic film and piece-thickness measuring methods " are really Fixed film thickness D determines the thickness of bonding layer.
The thickness of bonding layer is preferably more than 0.1 μm, more preferably more than 0.5 μm.So as to obtain enough engaging forces.Connect The thickness for closing layer is preferably less than 20 μm, more preferably less than 10 μm.When information is printed on from hectographic printing toward film from face, Or when film is inserted into mould, film bends can be suppressed.
[characteristic of film surface]
(smoothness)
Be provided with the surface of film the bonding layer side of porous layer surface (sometimes referred to as engaging side surface) it is flat Slippery s is according to JIS P 8155:2010 " paper and paperboard-smoothness method of testing-Wang Yanfa " are determined.Smoothness s is preferably 5 ~4000 seconds.So as to by it is in-molded film is attached on container body when, the air between film and container body Rapid discharge, obtains the tape label plastic containers of no air trapping.
Smoothness s is preferably less than 1000 seconds, more preferably less than 500 seconds.Accordingly, even if the size of label is very big, Also air can be discharged fast enough.Smoothness s is preferably more than 10 seconds, more preferably more than 20 seconds.So as to suppress Molten resin can not be filled in the phenomenon of the engagement side surface of film when in-molded.
(wetting tension)
Printed on the surface of the membrane by monolithic hectographic printing, web offset printing, intaglio printing, flexible printing, relief printing plate When the various mode of printings such as brush, silk-screen printing implement printing, according to JIS K 6768:1999 " plastic film and piece-wettings The moistened surface tension force W that force test method " is obtained is preferably more than 34mN/m, more preferably more than 42mN/m.So as to fill Ground is divided to show black acceptance.The wetting tension W on surface is preferably below 74mN/m, more preferably below 72mN/m.So as to enter During the punching processing of row film, the end that can suppress between film is mutually attached.In addition, the measure of wetting tension passes through in film On drip wetting tension test mixed liquor, the liquid on film is spread out with No.2 silk threads bar, according to the drop state after 2 seconds Judged.
(surface resistivity)
Surface resistivity R in 23 DEG C of 50%RHsAccording to JIS K6911:1995 " Thermocurable plastics general test sides The surface resistivity of method " is determined.The surface resistivity at least one surface of film is preferably 1 × 108~1 × 1012Ω.From And film can be prevented powered.When surface resistivity is in above range, anti-charging property can be obtained and hectographic printing is adapted to The excellent film of property.At least one surface of film can be the face for implementing Surface Machining.
When film is configured at into die inside, powered label inserter is also used sometimes.Powered label inserter is used DC high voltage generating means, makes to produce electrostatic on the side being in contact with container body in the face of film, passes through Electrostatic Absorption And film is fixed on mould.When using powered inserter, be in contact the face of side in the face of film with container body Surface resistivity is preferably 1 × 1012More than Ω.
<Post-processing>
[printing]
Information can be printed with film.The layer table on a surface side of porous layer can be arranged in layer contained by film Information is printed on face.Being not provided with layer contained by film can also in layer surface set on the side of the bonding layer of porous layer Print information.The printing sides such as intaglio printing, flexible printing, letterpress, silk-screen printing, electronic photo recording mode can be passed through Formula directly prints information on film.Using the prints such as ink-jet recording, hot tranfer recording mode, pressure-sensitive transfer recording mode During brush mode, the known receiving layer being adapted with various mode of printings can be further set on the surface of the membrane.Intaglio process The tractability of brush, ink-jet recording and electronic photo recording mode is excellent.Letterpress and flexible printing also can be correspondingly small The printing of batch.
Hectographic printing is when the wettability on the surface of film is excessively good, and ink easily bears water, makes ink be difficult to shift.Therefore, root It can not be applicable sometimes according to pattern.In addition, if the wettability on the surface of film is too poor, can be attached in the non-print portion of hectographic printing Inking, so as to cause substrate contamination.It therefore, it can form surface coating layer on the face of information for printing in film, will be thin The water contact angle on the surface of film is controlled in proper range.So as to optimize hectographic printing.It is also the same for surface free energy.
Printing ink used can be oiliness ink, or ultraviolet hardening ink.It is excellent from the viewpoint of resistance to nuzzling up property Choosing uses ultraviolet hardening ink.Ultraviolet hardening ink dry solidification by ultraviolet irradiation.Ultraviolet irradiation method is only If the method that ultraviolet hardening ink can solidify, is not specially limited, but can enumerate from such as metal halide lamp (200~400nm), Cooper-Hewitt lamp (180~250nm), high-pressure mercury-vapor lamp (250~365nm), blackout (350~360nm), The ultraviolet that UV-LED lamps (355~375nm) are irradiated is with 300~3000mJ/cm2, preferably 400~1000mJ/cm2Irradiation Measure to be irradiated.
Embodiment
Modulation example used below, sheetmolding example, embodiment, comparative example and test case further illustrate the present invention.Below Shown material, usage amount, ratio, operation etc. can be changed suitably without departing from the spirit of the present invention.Therefore, it is of the invention Scope be not limited to concrete example as shown below.As long as in addition, following described % does not illustrate to be quality %.
[test case]
<Thickness>
The thickness D of the film entirety obtained in sheetmolding example is based on JIS K 7130:1999 " plastic film and piece-thickness With level pressure thickness tester, (Co., Ltd. must find pleasure in system, machine name assay method "：PG-01J) it is determined.In addition, sheetmolding The thickness of each layer is measured by following step in the film obtained in example.First, by measure object sample in liquid nitrogen it is cold But less than -60 DEG C of temperature is arrived.Then, the measure object sample after cooling is placed on glass plate, relative to measure object Sample makes blade (Schick Japan Co. Ltd. systems, trade name：" De of プ ロ ラ イ Application Block レ mono- ") at right angles cut measure Subject sample, is made cross-section determination sample.Then, using scanning electron microscope (Jeol Ltd.'s system, machine Name：JSM-6490 the section of cross-section determination sample) is observed, image judges boundary line from, is determined as measure object Ratio of the thickness degree relative to film integral thickness D.Hereafter, integral thickness D is multiplied by by the observation of cross-section determination sample The above-mentioned ratio determined is determined to become the thickness degree of measure object.
<Flexible printing is evaluated>
Film obtained by each embodiment, comparative example is cut into 150mm width, bar samples are made.In bar samples A side surface on use flexible printing machine (trade name " TCL ", sun machinery production institute Co. Ltd. system) and ultraviolet curing The flexible ink of type (trade name " UV Off レ キ ソ CF ", T＆K TOKA Co. Ltd. systems) print trade name, manufacturer, sales company The text informations such as name, application method, points for attention and the pattern comprising bar code and outward appearance.Print and printed for 4 colors.It is printed on Implement in the environment of 23 DEG C of temperature, relative humidity 50%.In addition, print speed printing speed is 60m/ points.Then, make the sample after printing with 60m/ points of speed is by under ultraviolet radiation device (metal halide lamp, 100W/cm, 1 lamp, iGrafx Co. Ltd. systems), making The ink of printing surface is dried, and evaluation sample is made.
Ink transfer
The black transfering state of evaluation sample is judged with visually.The knot of black mobility self-evaluation is represented using following marks Really.
○：Transfer does not occur bad, well.
×：It there occurs that transfer is bad, it is bad.
Ink is closely sealed
The wide transparent adhesion band (Co., Ltd. of 18mm attached with 5cm length in the printing surface of evaluation sample NICHIBAN systems, product name：CT405AP-18), carry out peeling off at a high speed and visually confirming manually the stripping of ink, judged.Make The result of black closely sealed evaluation is represented with following marks.
○：100% area for implementing the part peeled off manually has remained ink.Or ink it is closely sealed too strong and make thermoplasticity Resin film is damaged.
△：50~100% area for implementing the part peeled off manually has remained ink.
×：0~50% area for implementing the part peeled off manually has remained ink.
<Hectographic printing is evaluated>
The film obtained in each embodiment, comparative example is cut into A3 sizes, offset press (RYOBI plants of formula meetings are used Society's system, machine name：RYOBI3300CR), UV hectographic printings ink (T＆K TOKA Co. Ltd. systems, product name：BC161) print 2000.UV (exposure 100mJ/cm are irradiated on resulting printed article2), make ink solidification that evaluation sample is made.
Ink transfer
With the black transfering state for visually confirming evaluation sample.The result of black mobility self-evaluation is represented using following marks.
○：Transfer does not occur bad, well.
×：It there occurs that transfer is bad, it is bad.
Ink is closely sealed
The wide transparent adhesion band (Co., Ltd. of 18mm is adhered to 5cm length on the printing surface of evaluation sample NICHIBAN systems, product name：CT405AP-18), carry out peeling off manually at a high speed and with visually confirming black stripping.Use following marks Remember to represent the result of black closely sealed evaluation.
○：100% area for implementing the part peeled off manually has remained ink.Or ink it is closely sealed too strong and make thermoplasticity Resin film is damaged.
△：50~100% area for implementing the part peeled off manually has remained ink.
×：0~50% area for implementing the part peeled off manually has remained ink.
<In-molded adaptability>
By the film punching processing obtained in each embodiment, comparative example into horizontal 60mm, vertical 110mm rectangle, band mark is made Sign the label used in the manufacture of plastic containers.One 's that ready label is fixed in a pair of moulds of blow molding On medial surface.Above-mentioned mould use can be molded the mould of 400ml content measuring bottles.Label is configured to make the hot sealing layer direction of label Cavity side, is fixed on mould using attraction.
Then, by high density polyethylene (HDPE) (trade name " ノ バ テ Star Network HD HB420R ", Japanese polyethylene between mould Co. Ltd. system, MFR (JIS K 7210：1999)=0.2g/10 divides, melts peak temperature (JIS K 7121:2012)=133 DEG C, Crystallization peak temperature (JIS K 7121：2012)=115 DEG C, density=0.956g/cm3) melted and squeezed with 160 DEG C Molded billet.Then, by after mould shape, 4.2kg/cm is supplied into parison2Compressed air.Parison is set to expand 16 Second, while the parison is sealed at mould and is turned into container-like, the parison and label are fused.Hereafter, will shaping in mould Thing is cooled down, and is opened mould and is obtained tape label plastic containers.Mould chilling temperature is 20 DEG C, the injection circulation time is 34 seconds/time.
160 DEG C of zygosities
By visual observation come the outward appearance of the tape label plastic containers obtained by confirming, connect using aftermentioned mark to evaluate 160 DEG C Conjunction property.
200 DEG C of zygosities
In addition to being extruded as parison shape with 200 DEG C of melting high density polyethylene (HDPE)s, pass through the evaluation with 160 DEG C of zygosities Used tape label plastic containers identical method, is made tape label plastic containers used in the evaluation of 200 DEG C of zygosities.
By visual observation come the outward appearance of the tape label plastic containers obtained by confirming, connect using aftermentioned mark to review 200 DEG C Conjunction property.
○：Engage without foaming and aesthetically.
△：Engage but bubbled with the ratio for having less than 1 in 4.
×：Bond strength is weak or is bubbled with the ratio for having more than 2 in 4.
Orange peel effect is evaluated
With the outward appearance of tape label plastic containers used in the visual evaluation for confirming 200 DEG C of zygosities, commented with aftermentioned mark Valency orange peel effect.
○：It is concavo-convex also unobvious even if irradiating skew ray.
△：Irradiate concavo-convex obvious during skew ray, concavo-convex interval is less than 0.5mm.
×：Irradiate concavo-convex obvious during skew ray, it is concavo-convex at intervals of more than 0.5mm.
[using material]
Material used in film forming and its physical property are shown in table 1.The average grain diameter of inorganic fine powder is from BET The particle diameter that specific surface area is tried to achieve, D50 represents the accumulated value of MicrotrackHRA (Nikkiso Company Limited's system) volume distributed median Particle diameter (sometimes referred to as volume average particle size) in 50%, D90 represents that the particle diameter in similarly accumulated value 90% (is sometimes referred to as body Product average grain diameter).
[table 1]
Composition, manufacturing condition, the characteristic of film and the evaluation result of the film of embodiment 1~12 are shown in table 2.Compare Composition, manufacturing condition, the characteristic of film and the evaluation result of the film of example 1~5 are shown in table 3.In table 2 and table 3, with connecing Close and implement surface treatment on the face of layer opposite side.In addition, wetting tension and surface resistivity are directed to the side without bonding layer It is measured.In addition, in table 2 and 3, the "-" in flexible printing adaptability and hectographic printing adaptability represents not evaluated.
Embodiment 1：
(film forming)
As the material of porous layer, by the high density polyethylene (HDPE) (A-1) described in table 1, powdered whiting (B-1), add Plus agent (dispersant and antioxidant) is with mass ratio 30:70:1 is mixed, and it is being set as carrying out in 180 DEG C of extruder There is provided to the T moulds for being set as 190 DEG C after mixing melting, sheet is extruded as.The piece of extrusion is cooled to about 40 with chill roll DEG C obtain 296 μm of tensionless winkler foundation piece.Then, tensionless winkler foundation piece is again heated to after 110 DEG C, it is vertical using the difference edge of roller group Direction carries out 2 times of stretchings (MD stretchings), then and Tenter oven is again heated to after 128 DEG C, using stenter along 2 times of transverse direction progress Stretch (TD stretchings).Hereafter, adjust to 130 DEG C heat setting area made annealing treatment, be cooled to about 60 DEG C by chill roll, cut Lower ear, obtains the biaxial stretch-formed HDPE films being made up of porous layer individual layer.
The thickness D of the film of embodiment 1 is 198 μm, thermal resistance value RtFor 0.21m2K/W, the density p of porous layer is 0.629g/m3, void content p is 64%, and emptying aperture length L is 126 μm, and smoothness s is 111 seconds, sheet resistance value RsFor 1.0 × 1016Ω。
(in-molded to evaluate)
On the film of embodiment 1, to being obtained in aforementioned manners so that 160 DEG C and 200 DEG C progress of parison temperature are in-molded Tape label plastic containers evaluated.160 DEG C of zygosities：0th, 200 DEG C of zygosities：0th, orange peel effect：Zero, well.
Embodiment 2~3, comparative example 1：
(film forming)
In embodiment 1, in addition to MD draft temperatures and TD draft temperatures are changed by table 2 or table 3, with implementation Example 1 is identical, and the film of embodiment 2~3 and comparative example 1 is made.In addition, the film of comparative example 1 substantially has stretching uneven, it is judged as It is not durable.Accordingly, with respect to the physics value of the film undetermined film of comparative example 1.In addition, being fitted for IML adaptability, flexible printing Answering property and hectographic printing adaptability are not also evaluated.
(in-molded to evaluate)
On the film of obtained embodiment 2~3, (sometimes referred to as in-molded is evaluated to in-molded adaptability Evaluate).It is same as Example 1 to obtain zygosity, orange peel effect good result.
Embodiment 4, comparative example 2：
(film forming)
In embodiment 1, the pulling speed of chill roll is improved, except the thickness of tensionless winkler foundation piece is carried out as shown in table 2 or table 3 It is same as Example 1 beyond change, it is made embodiment 4, the film of comparative example 2.
(in-molded to evaluate)
In-molded evaluate is carried out to the film being made.Result is included in table 2 or table 3.When emptying aperture length is less than 20 μ During m, thermal insulation is not enough, the reduction of IML adaptability.
Embodiment 5~6：
(film forming)
In embodiment 1, except composition A thermoplastic resin, composition B powdered whiting are carried out as shown in table 2 It is same as Example 1 beyond change, the film of embodiment 5~6 is made.
(in-molded to evaluate)
In-molded evaluate is implemented to the film being made.Result is included in table 2.Although changing matching somebody with somebody for porous layer It is mixed, but obtained the evaluation unlike the difference of embodiment 1.
Embodiment 7：
(film forming)
In embodiment 1, by the thermoplastic resin (A-1) in porous layer, powdered whiting (B-1), additive (dispersant And antioxidant) compounding amount by being changed table 2 Suo Shi, adjusting the thickness and stretching condition of tensionless winkler foundation piece makes porous layer Void content is changed into 35~40%, and the film of embodiment 7 is made.
(in-molded to evaluate)
In-molded evaluate is implemented to the film being made.Result is included in table 2.Understand：When in reduction porous layer Inorganic fine powder content when, be adjusted to ensure that emptying aperture length as long as carrying out improving stretching ratio etc., then IML can be presented Adaptability.But generate orange peel effect of the interval less than 0.5mm of bumps.
Comparative example 3：
(film forming)
As the material of porous layer, by the high density polyethylene (HDPE) (A-1) described in table 1, powdered whiting (B-1), add Plus agent (dispersant and antioxidant) is with mass ratio 75:25:1 is mixed, and carries out kneading in equidirectional two axles kneading machine To thermoplastic resin composition's particle of porous layer.On the other hand, by high density polyethylene (HDPE) (A-1), powdered whiting (B- 1), additive is with mass ratio 80:20:0.5 is mixed, and in equidirectional two axles kneading machine knead obtaining superficial layer Thermoplastic resin composition's particle.
Then, by thermoplastic resin composition's particle of porous layer and the thermoplastic resin composition of superficial layer Grain is melted in different extruders respectively.The temperature of extruder is set as 180 DEG C.Then, by the Porous of melting Layer thermoplastic resin composition with melt superficial layer thermoplastic resin composition be supplied to be set as 190 DEG C one Platform co-extrusion compression mould, is laminated into superficial layer/porous layer/superficial layer in mould, obtains 2 kinds three layers of 574 μm of thickness without drawing Stretch piece.
Tensionless winkler foundation piece is again heated to after 110 DEG C, 2 times of stretchings is carried out along longitudinal direction using the difference of roller group, connects And be again heated to using Tenter oven after 128 DEG C, 2 times of stretchings are carried out along transverse direction using stenter.Afterwards, to adjust to 130 DEG C Heat setting area made annealing treatment, about 60 DEG C are cooled to chill roll, cutting ear, to obtain 2 kinds of three layers of Biaxially stretched HDPE thin Film.
The thickness D of the film of comparative example 3 is 60 μm, thermal resistance value RtFor 0.07m2K/W, the thickness d of porous layer is 49 μ M, density p is 0.677g/m3, void content p is 37%, and emptying aperture length L is 22 μm, and smoothness s is 109 seconds, sheet resistance value RsFor 1.0×1016Ω。
(in-molded to evaluate)
In-molded evaluation is implemented to the film being made.It the results are shown in table 3.The content of inorganic fine powder is low It is that to embody zygosity only to improve stretching ratio be inadequate in the in-molded film of 35 mass % existing type, and produces The concavo-convex orange peel effect at intervals of more than 0.5mm.
Comparative example 4：
(film forming)
It is identical with comparative example 3 in addition to the thickness of 2 kinds of three layers of tensionless winkler foundation pieces is set into 1248 μm, comparative example 4 is made 2 kinds of three layers of Biaxially stretched HDPE films.The thickness D of the film of comparative example 4 is 130 μm, thermal resistance value RtFor 0.12m2K/W is more The thickness d of hole matter layer is 118 μm, and density p is 0.677g/m3, void content p is 39%, and emptying aperture length L is 51 μm, and smoothness s is 101 seconds, sheet resistance value RsFor 1.1 × 1016Ω。
(in-molded to evaluate)
Film on being made has carried out in-molded evaluation.It the results are shown in table 3.With the film phase of comparative example 3 Compare by increasing thickness d, emptying aperture length L becomes big, shows IML adaptability.However, emptying aperture size is big, bumps are generated At intervals of more than 0.5mm orange peel effect.
Comparative example 5：
(film forming)
In embodiment 1, it is the thermoplastic resin (A-1) in porous layer, powdered whiting (B-1), additive is (scattered Agent and antioxidant) compounding amount be changed to 20:80:1, film is made in trial.However, the thermoplastic resin as decentralized medium It is less, become fragile with the formed in mould tensionless winkler foundation pieces of T, it is impossible to carry out vertical stretching.Accordingly, with respect to the film of comparative example 5, undetermined is thin The physics value of film.In addition, also not evaluated on IML adaptability, flexible printing adaptability and hectographic printing adaptability.
Embodiment 8：
(film forming)
As the material of porous layer, by the high density polyethylene (HDPE) (A-1) described in table 1, powdered whiting (B-1), add Plus agent (dispersant and antioxidant) is with mass ratio 30:70:1 is mixed, and carries out kneading in equidirectional two axles kneading machine To thermoplastic resin composition's particle of porous layer.On the other hand, by high density polyethylene (HDPE) (A-1), powdered whiting (B- 1), additive is with mass ratio 80:20:0.5 is mixed, and in equidirectional two axles kneading machine knead obtaining superficial layer Thermoplastic resin composition's particle.
Then, by the thermoplastic resin composition of thermoplastic resin composition's particle of porous layer, superficial layer Grain, the resin as bonding layer are ethylene-alpha-olefin copolymer (Japan Polyethylene Corp.'s system, the ネ Le KF270 (commodity of カ mono- Name), fusing point：100 DEG C) melted respectively in different extruders.The temperature of extruder is all set to 180 DEG C.Then, By the thermoplastic resin composition of the porous layer of melting, thermoplastic resin composition, the Yi Jirong of the superficial layer of melting The ethylene-alpha-olefin copolymer melted, which is supplied to, is set in 190 DEG C of a co-extrusion compression mould, and superficial layer/many is laminated into mould Hole matter layer/bonding layer, extrudes slabbing.Obtained piece is cooled to about 40 DEG C with chill roll and obtains 3 kinds three layers of 131 μm of thickness Tensionless winkler foundation piece.
Tensionless winkler foundation piece is again heated to after 129 DEG C, 2 times of stretchings is carried out along longitudinal direction using the difference of roller group, connects And be again heated to Tenter oven after 135 DEG C, 2 times of stretchings are carried out along transverse direction with stenter.Hereafter, to adjust to 130 DEG C of heat Setting area is made annealing treatment, and about 60 DEG C are cooled to chill roll, is cut ear and is obtained 3 layer of three axle stretching HDPE film.
The film of embodiment 8 can be peeled off to take out porous layer with hand.The overall thickness D of film is 67 μm, heat Resistance RtFor 0.02m2K/W, the density p of porous layer is 1.060g/m3, void content p is 40.6%, and emptying aperture length L is 22 μ M, smoothness s are 1284 seconds, sheet resistance value RsFor 9.7 × 1015Ω。
(cross-section)
The film of embodiment 8 is wrapped up with epoxy resin, the sample of cross-section determination is cut into slicer.Then, make With scanning electron microscope (Jeol Ltd.'s system, machine name：JSM-6490 the section of above-mentioned sample) is observed, from sight Examine image discriminating boundary line.The thickness d of the porous layer thickness D overall relative to film ratio is 42%.According to above-mentioned ratio The thickness d of porous layer is defined as 55 μm by rate.
In addition, image determines the volume ratio of each composition according to the observation.The volume ratio of composition (A-1) is 58 volume %, The volume ratio of composition (B-1) is 42 volume %.The density of composition (A-1) is 0.896g/cm3, the density of composition (B-1) is 2.890g/cm3.The volume ratio of each composition determined using image according to the observation calculates containing for each composition with the density of each composition Found during amount, the content of composition (A-1) is 29.98 mass %, and composition (B-1) content is 70.02 mass %.This and porous layer Raw material compounding ratio it is very consistent.
(in-molded to evaluate)
In-molded evaluate is carried out for the film being made.These results are included in table 2.Because emptying aperture length is close 20 μm, thermal insulation is low, and IML adaptability is expressed as △.On the other hand, stretching ratio is 2 × 2 times, and the size of emptying aperture is smaller, does not give birth to Into orange peel effect.By setting bonding layer to improve smoothness s, but do not find there is air to mix between bonding layer and plastic containers Enter.
Embodiment 9~11：
(film forming)
As the material of porous layer, by the high density polyethylene (HDPE) (A-1) described in table 1, powdered whiting (B-1), add Plus agent (dispersant and antioxidant) is with mass ratio 30:70:1 is mixed, and is kneaded with equidirectional two axles kneading machine Thermoplastic resin composition's particle of porous layer.On the other hand, by high density polyethylene (HDPE) (A-1), powdered whiting (B- 1), additive is with mass ratio 80:20:0.5 is mixed, and in same kneading machine knead the thermoplasticity for obtaining superficial layer Resin composition pellet.
Then, by the thermoplastic resin composition of thermoplastic resin composition's particle of porous layer and superficial layer Grain is melted in different extruders respectively.The temperature of extruder is set as 180 DEG C.Then, by the Porous of melting Layer thermoplastic resin composition with melt superficial layer thermoplastic resin composition be supplied to be set as 190 DEG C one Platform co-extrusion compression mould, is laminated into as superficial layer/porous layer/superficial layer in mould, is extruded as sheet.Resulting piece is used Chill roll is cooled to about 40 DEG C, obtains 305 μm of tensionless winkler foundation piece.
Tensionless winkler foundation piece is again heated to after 110 DEG C, using roller group difference along longitudinal direction stretch 2 times, then It is again heated to using Tenter oven after 128 DEG C, 2 times is stretched along transverse direction using stenter.Hereafter, adjusting to 130 DEG C of heat Setting area is made annealing treatment, and about 60 DEG C are cooled to chill roll, ear is split, two kinds of three layers of biaxial stretch-formed HDPE are obtained thin Film.
Two kinds of 3 layers of 2 axles stretching HDPE films of embodiment 9 can be peeled off to take out porous layer with manual.Film is overall Thickness D be 211 μm, thermal resistance value RtFor 0.22m2K/W, the thickness d of porous layer are 202 μm, density p is 0.607g/m3、 Void content P is that 65%, emptying aperture length L is 137 μm.Moreover, the wetting tension W on surface is 31mN/m.
(surface treatment)
Embodiment 9 film one side with 45W/m2/ point intensity implement Corona discharge Treatment, obtain embodiment 10 Film.The wetting tension W on surface is 42mN/m.In addition, embodiment 9 film two sides with 45W/m2/ point intensity implement Corona discharge Treatment, then, by following (a), 0.4 mass % (b) and 0.5 mass % (c) comprising 0.5 mass % The aqueous solution (surface conditioning agent) be coated in size press mode so that in per unit area (m2) contain after drying 0.01g anti-live agent, is dried at 70 DEG C, obtains the film of embodiment 11.The wetting tension W on surface is 70mN/m.
(surface conditioning agent)
Following material (a)~(c) is used to surface conditioning agent.
(a) acrylic acid terpolymer containing quaternary nitrogen
The acrylic acid terpolymer containing tertiary carbon being made up of (a-1)~(a-3) unit is synthesized, potassium monochloroacetate is used Level Four is carried out, amphiphilic polymers are obtained.In addition, by (a-1) in the acrylic acid terpolymer containing tertiary carbon~(a-3's) Content is shown with each composition.
(a-1) N, N'- dimethyl aminoethyl Methacrylamide (emerging people's Co. Ltd. system)：40 mass %
(a-2) n-butyl acrylate (Kanto Kagaku K. K.'s system)：35 mass %
(a-3) octadecyl acrylate (Kanto Kagaku K. K.'s system)：25 mass %
(b) polyethyleneimine (Nippon Shokubai Co., Ltd's system, エ Port ミ Application -1000 (trade name))
(c) epoxychloropropane addition product (Nippon PMC K. K.'s system, the WS-4024 (commodity of water-soluble polyamine polyamide Name))
(in-molded evaluation)
On the film of embodiment 9~11, found when carrying out in-molded evaluation, the 160 DEG C of zygosities of each are equal For：0th, 200 DEG C of zygosities are：0th, orange peel effect is：Zero, it is all very good.
(evaluation of flexible printing)
The one side of the film in Corona discharge Treatment face and embodiment 11 to the film of embodiment 10 carries out flexible printing and commented Valency, black metastatic and black adaptation are zero, are good.
(hectographic printing evaluation)
The Corona discharge Treatment face of the film of embodiment 10 is attempted to carry out hectographic printing evaluation, due to quiet between piece and piece Electricity is pasted and can not sent into, therefore have ceased evaluation.Hectographic printing evaluation has been carried out to the one side of the film of embodiment 11.Printing 2000, black metastatic, ink are closely sealed all very good.
Embodiment 12：
(film forming)
In embodiment 1, in addition to the compounding amount for the additive being compounded in porous layer is changed into 6 mass parts with implementation Example 1 is identical, obtains the film of embodiment 12.White powder is found on the membrane surface.
(in-molded evaluation)
In-molded evaluation has been carried out to obtained film.Result is included in table 2.In-molded adaptability is with implementing Example 2 is identical.
(evaluation of flexible printing)
With 45W/m on the one side of resulting film2/ point intensity implement Corona discharge Treatment, at corona discharge Reason face has carried out flexible printing evaluation, but black metastatic and black adaptation are bad.Hectographic printing evaluation is not carried out.
[table 2]
[table 3]
It can be seen from the result of embodiment 1~12, the mass % of thermoplastic resin 25~65 is included and inorganic micro- by possessing The mass % of fine powder 35~75 (two kinds composition add up to 100 mass parts) and emptying aperture length L are more than 20 μm of porous layer, Obtain showing good zygosity and with the film for the property for being not likely to produce orange peel effect in-molded.Consider this be because To inhibit the heat for being discharged to mould through label from parison in in-molded.The emptying aperture length L of porous layer is found in addition It can be adjusted by suppressing stretching ratio and being molded.
On the other hand, from the point of view of embodiment 7,8 and the result of comparative example 3,4, on it is in-molded when the tangerine peel that produces show As, it is believed that unrelated with thickness, the influence of stretching ratio is larger, and emptying aperture size brings influence.Think in porous layer comprising big Small size emptying aperture is measured, then is less likely to occur the distortion of porous layer.
In addition, the fusing point and film and plastic containers phase that pass through thermoplastic resin contained by the outmost surface by plastic containers The fusing point of thermoplastic resin contained by the layer of contact is adjusted to meet specific relation, and label can be also obtained even if bonding layer is not provided with The excellent tape label plastic containers such as zygosity.In addition, if rising wetting tension by corona discharge, then print can be assigned Brush adaptability, and then by setting appropriate surface coating layer, obtains that the anti-charging property in surface is excellent, be able to maintain that good print suitable The film of answering property.
Industrial applicability
Obtain that void content is high, emptying aperture size is small and uniform film according to the present invention, so that the parison when in-molded Under conditions of temperature is relatively low also can accomplished high bonding force, while seldom produce orange peel effect tape label plastic containers.Cause This is suitable to the manufacture for attaching the tape label plastic containers of thermoplastic resin membrane.Also, pass through appropriate surface treatment energy Enough assign is adapted to printing, can suppress the malfunction as caused by electrostatic in film processed.Therefore printing is also applied for use The purposes such as paper, label.

Claims (29)

1. a kind of tape label plastic containers, it is characterised in that it is pasted with containing the thin of thermoplastic resin by in-molded Film, the film has the porous layer of at least 1 layer condition for meeting following (A) and (B),
In the section parallel with the thickness direction of the porous layer since the surface of following inorganic fine powders to sky Ultimate range untill hole wall is less than 50 μm：
(A) porous layer includes the mass parts of thermoplastic resin 25~65 and the mass parts of inorganic fine powder 35~75；
(B) the emptying aperture length L of the porous layer shown in following formula (1) is more than 20 μm,
L=d × (ρ0-ρ)/ρ0... formula (1)
In the formula (1), L is the emptying aperture length [μm] of the porous layer, and d is the thickness [μm] of the porous layer, and ρ is institute State the density [g/cm of porous layer3], ρ0For the real density [g/cm of the porous layer3]。
2. tape label plastic containers according to claim 1, wherein, the surface resistivity at least one face of the film RsIt is 1 × 10 under conditions of 23 DEG C of 50%RH8Ω~1 × 1012Ω。
3. a kind of tape label plastic containers, it is characterised in that it is pasted with containing the thin of thermoplastic resin by in-molded Film, the film has the porous layer of at least 1 layer condition for meeting following (A) and (B),
The surface resistivity R at least one face of the filmsIt is 1 × 10 under conditions of 23 DEG C of 50%RH8Ω~1 × 1012 Ω：
(A) porous layer includes the mass parts of thermoplastic resin 25~65 and the mass parts of inorganic fine powder 35~75；
(B) the emptying aperture length L of the porous layer shown in following formula (1) is more than 20 μm,
L=d × (ρ0-ρ)/ρ0... formula (1)
In the formula (1), L is the emptying aperture length [μm] of the porous layer, and d is the thickness [μm] of the porous layer, and ρ is institute State the density [g/cm of porous layer3], ρ0For the real density [g/cm of the porous layer3]。
4. according to tape label plastic containers according to any one of claims 1 to 3, wherein, the film is also met following (C) Condition：
(C) thickness d of the porous layer is the 10~100% of the thickness D of the film.
5. according to tape label plastic containers according to any one of claims 1 to 3, wherein, the porous layer is relative to institute Total 100 mass parts for stating thermoplastic resin and the inorganic fine powder include the mass parts of additive 0.1~5.
6. according to tape label plastic containers according to any one of claims 1 to 3, wherein, formula (2) institute of the porous layer The void content p shown is 15~75%：
P=(ρ0-ρ)/ρ0× 100 ... formulas (2)
In the formula (2), p is the void content [%] of the Porous, and ρ is the density [g/cm of the porous layer3], ρ0For institute State the real density [g/cm of porous layer3]。
7. according to tape label plastic containers according to any one of claims 1 to 3, wherein, contained by the porous layer The thermoplastic resin is using polyolefin as main component.
8. according to tape label plastic containers according to any one of claims 1 to 3, wherein, the porous layer edge at least one Direction of principal axis is stretched.
9. according to tape label plastic containers according to any one of claims 1 to 3, wherein, the thickness D of the film for 40~ 250μm。
10. according to tape label plastic containers according to any one of claims 1 to 3, it also has in the porous layer The superficial layer set on one surface side.
11. according to tape label plastic containers according to any one of claims 1 to 3, wherein, in the described porous of the film The surface printing information of the layer set on one surface side of matter layer.
12. according to tape label plastic containers according to any one of claims 1 to 3, it also has in the porous layer The bonding layer set on one surface side,
The surface of the bonding layer according to JIS P 8119:The 1998 Wang Yan formula smoothnesses s determined are 5~4000 seconds.
13. tape label plastic containers according to claim 12, it also has in another surface side of the porous layer The superficial layer of upper setting.
14. tape label plastic containers according to claim 12, wherein, the film the porous layer it is another The surface printing information of the layer set on individual surface side.
15. tape label plastic containers according to claim 12, wherein, the surface of the tielayer side of the film Surface resistivity RsIt is 1 × 10 under conditions of 23 DEG C of 50%RH12More than Ω.
16. according to tape label plastic containers according to any one of claims 1 to 3, wherein, the following formula (3) of the film Shown thermal resistance value RtFor 0.05m2More than K/W：
Rt=D × 10-6/ λ ... formulas (3)
In the formula (3), RtFor the thermal resistance value [m of the film2K/W], D is the thickness [μm] of the film, and λ is described thin The thermal conductivity [W/mK] of film.
17. according to tape label plastic containers according to any one of claims 1 to 3, it meets the relation of following formula (4)：
Tf-10≤Tv≤Tf+60 ... formulas (4)
In the formula (4), Tv is the thermoplastic resin contained by the outmost surface of the container body of the tape label plastic containers Fusing point, Tf is the fusing point of the thermoplastic resin contained by the layer being in contact with the container body of the film.
18. a kind of in-mold shaping label, it is characterised in that it includes the film containing thermoplastic resin, the film has extremely Lack 1 layer of porous layer for meeting following (A) and (B) condition,
The surface resistivity R at least one face of the filmsIt is 1 × 10 under conditions of 23 DEG C of 50%RH8Ω~1 × 1012 Ω：
(A) porous layer includes the mass parts of thermoplastic resin 25~65 and the mass parts of inorganic fine powder 35~75；
(B) the emptying aperture length L of the porous layer shown in following formula (1) is more than 20 μm,
L=d × (ρ0-ρ)/ρ0... formula (1)
In the formula (1), L is the emptying aperture length [μm] of the porous layer, and d is the thickness [μm] of the porous layer, and ρ is institute State the density [g/cm of porous layer3], ρ0For the real density [g/cm of the porous layer3]。
19. in-mold shaping label according to claim 18, wherein, the film also meets the condition of following (C)：
(C) thickness d of the porous layer is the 10~100% of the thickness D of the film.
20. the in-mold shaping label according to claim 18 or 19, wherein, the porous layer is relative to the thermoplasticity Total 100 mass parts of resin and the inorganic fine powder include the mass parts of additive 0.1~5.
21. the in-mold shaping label according to claim 18 or 19, wherein, the sky shown in the formula (2) of the porous layer Porosity p is 15~75%：
P=(ρ0-ρ)/ρ0× 100 ... formulas (2)
In the formula (2), p is the void content [%] of the Porous, and ρ is the density [g/cm of the porous layer3], ρ0For institute State the real density [g/cm of porous layer3]。
22. the in-mold shaping label according to claim 18 or 19, wherein, the contained thermoplastic in the porous layer Property resin is using polyolefin as main component.
23. the in-mold shaping label according to claim 18 or 19, wherein, a porous layer edge at least direction of principal axis quilt Stretching.
24. the in-mold shaping label according to claim 18 or 19, wherein, the thickness D of the film is 40~250 μm.
25. the in-mold shaping label according to claim 18 or 19, it also has in a surface side of the porous layer The superficial layer or surface coating layer of upper setting.
26. the in-mold shaping label according to claim 18 or 19, wherein, the one of the porous layer of the film The surface printing information of the layer set on individual surface side.
27. the in-mold shaping label according to claim 18 or 19, it also has in a surface side of the porous layer The bonding layer of upper setting,
The surface of the bonding layer according to JIS P 8119:The 1998 Wang Yan formula smoothnesses s determined are 5~4000 seconds.
28. in-mold shaping label according to claim 27, wherein, the table on the surface of the tielayer side of the film Surface resistivity RsIt is 1 × 10 under conditions of 23 DEG C of 50%RH12More than Ω.
29. the in-mold shaping label according to claim 18 or 19, wherein, the heat shown in the following formula (3) of the film Resistance RtFor 0.05m2More than K/W：
Rt=D × 10-6/ λ ... formulas (3)
In the formula (3), RtFor the thermal resistance value [m of the film2K/W], D is the thickness [μm] of the film, and λ is described thin The thermal conductivity [W/mK] of film.
CN201480000827.0A 2014-03-03 2014-03-03 Film and tape label plastic containers Active CN105102224B (en)

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